Acid dyes, process for the production thereof and their use

ABSTRACT

Dyes of formula (1) 
     
       
         
         
             
             
         
       
     
     process for their production and their use.

The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.

Acid dyes with pyridine couplers are known from prior art and can be used as colorants in different applications, see for example U.S. Pat. No. 3,959,250 A1, U.S. Pat. No. 5,468,848 A1, JP 1 197578 A and WO 2007/045825 A2.

However, in the context of the dyeing and printing of hydroxyl- and/or carboxamido-containing material the known dyes have a number of technical disadvantages, which require improvement.

One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.

Surprisingly, it has now been found that the dyes of formula (1) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.

If heavy metals are present at all in the dyes of the present invention they do not result from being integral part of the dye but are coursed by the production process in general. Reasons in general for these impurities can be impurities resulting from educts and catalysts being used in the respective reactions—the levels of such impurities can be managed and be kept well below those recommended e.g. by ETAD® and would thus be below 100 ppm for Cr, below 250 ppm for Cu and below 200 ppm for Ni just to mention the values for the metals mentioned above. This is a significant improvement as compared to dyes where such metals are present at molar levels.

The present invention refers to dyes of the formula (1) and mixtures thereof

wherein R¹, R², R³ and R⁴ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M whereby at least two of them are SO₃M, R⁵, R⁶, R⁷ and R⁸ independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO₃M or alkylureido, R⁹ and R¹⁵ independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R¹⁰ and R¹⁶ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R¹¹, R¹², R¹³, R¹⁴, R¹⁷, R¹⁸, R¹⁹, R²⁰ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, the dyes of formula (1) have two to six sulfonic acid groups and whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R¹¹, R¹², R¹³ and R¹⁴, respectively can be positioned ortho or para to R⁹, meaning that when the amino rest bearing the substituents R¹¹ and R¹² is positioned ortho to R⁹, the amino rest bearing the substituents R¹³ and R¹⁴ is positioned para to R⁹, and vice versa; and the same applies to the amino rests bearing the substituents R¹⁷, R¹⁸, R¹⁹ and R²⁰, respectively that can be positioned ortho or para to R¹⁵, meaning that when the amino rest bearing the substituents R¹⁷ and R¹⁸ is positioned ortho to R¹⁵, the amino rest bearing the substituents R¹⁹ and R²⁰ is positioned para to R¹⁵, and vice versa.

This invention refers to all tautomeric and geometric isomers of the dyes of formula (1) and mixtures thereof.

Alkyl groups appearing in this invention may be straight-chain or branched and are (C₁-C₁₂)-alkyl groups, preferably (C₁-C₈)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.

The same applies to alkoxy groups which accordingly are preferably (C₁-C₈)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (C₁-C₈)-thioalkoxy, for example —SCH₃ or —SC₂H₅.

Cycloalkyl groups are preferably (C₃-C₈)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purpose of the present invention substituted cycloalkyl groups and unsaturated cycloalkyl groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Alkenyl groups may be straight-chain or branched and are preferably (C₂-C₆)-groups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl.

Aryl groups appearing in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole. The terms heteroaryl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The term heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalky)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(C₁-C₄)-alkylammonium.

Particularly preferred embodiments of the present invention are dyes of formula (1a) and mixtures thereof

wherein R^(1a), R^(2a), R^(3a) and R^(4a) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9a) and R^(15a) independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10a) and R^(16a) independent of one another is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl, R^(11a), R^(12a) R^(13a), R^(14a), R^(17a), R^(18a), R^(19a) and R^(20a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In particularly preferred dyes of formula (1a):

R^(1a), R^(2a), R^(3a) and R^(4a) independent of each other is SO₃M, hydrogen, alkyl, alkoxy or halogen—whereby at least two of them are SO₃M, R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9a) and R^(15a) independent of each other is cyano or carbamoyl, R^(10a) and R^(16a) is methyl, R^(11a), R^(12a) R^(13a), R^(14a), R^(17a), R^(18a), R^(19a) and R^(20a) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of particularly preferred dyes of the formula (1a) are the compounds of formulae (1a¹ to 1a⁴⁶²) and mixtures thereof:

Struc- R^(14a)/ ture R^(1a) R^(2a) R^(3a) R^(4a) R^(5a)/R^(7a) R^(6a)/R^(8a) R^(9a)/R^(16a) R^(11a)/R^(17a) R^(12a)/R^(18a) R^(13a)/R^(19a) R^(20a) 1a¹ SO₃H SO₃H H H Methyl Methyl CN Methyl H Methyl H 1a² SO₃H H H SO₃H 1a³ SO₃H SO₃H H H Methyl Methyl CN Ethyl H Ethyl H 1a⁴ SO₃H H H SO₃H 1a⁵ SO₃H SO₃H H H Methyl Methyl CN Propyl H Propyl H 1a⁶ SO₃H H H SO₃H 1a⁷ SO₃H SO₃H H H Methyl Methyl CN Butyl H Butyl H 1a⁸ SO₃H H H SO₃H 1a⁹ SO₃H SO₃H H H Methyl Methyl CN Pentyl H Pentyl H 1a¹⁰ SO₃H H H SO₃H 1a¹¹ SO₃H SO₃H H H Methyl Methyl CN Hexyl H Hexyl H 1a¹² SO₃H H H SO₃H 1a¹³ SO₃H SO₃H H H Methyl Methyl CN Cyclobutyl H Cyclobutyl H 1a¹⁴ SO₃H H H SO₃H 1a¹⁵ SO₃H SO₃H H H Methyl Methyl CN Cyclopentyl H Cyclopentyl H 1a¹⁶ SO₃H H H SO₃H 1a¹⁷ SO₃H SO₃H H H Methyl Methyl CN Cyclohexyl H Cyclohexyl H 1a¹⁸ SO₃H H H SO₃H 1a¹⁹ SO₃H SO₃H H H Methyl Methyl CN 2-Methyl H 2-Methyl H 1a²⁰ SO₃H H H SO₃H cyclohexyl cyclohexyl 1a²¹ SO₃H SO₃H H H Methyl Methyl CN 3-Methyl H 3-Methyl H 1a²² SO₃H H H SO₃H cyclohexyl cyclohexyl 1a²³ SO₃H SO₃H H H Methyl Methyl CN Isopropyl H Isopropyl H 1a²⁴ SO₃H H H SO₃H 1a²⁵ SO₃H SO₃H H H Methyl Methyl CN Sec-butyl H Sec-butyl H 1a²⁶ SO₃H H H SO₃H 1a²⁷ SO₃H SO₃H H H Methyl Methyl CN 2- H 2- H 1a²⁸ SO₃H H H SO₃H Methylbutyl Methylbutyl 1a²⁹ SO₃H SO₃H H H Methyl Methyl CN 1- H 1- H 1a³⁰ SO₃H H H SO₃H Ethylpropyl Ethylpropyl 1a³¹ SO₃H SO₃H H H Methyl Methyl CN 1,2- H 1,2- H 1a³² SO₃H H H SO₃H Dimethyl Dimethyl propyl propyl 1a³³ SO₃H SO₃H H H Methyl Methyl CN Tert-butyl H Tert-butyl H 1a³⁴ SO₃H H H SO₃H 1a³⁵ SO₃H SO₃H H H Methyl Methyl CN 3-Methyl H 3-Methyl H 1a³⁶ SO₃H H H SO₃H butyl butyl 1a³⁷ SO₃H SO₃H H H Methyl Methyl CN Pentan-2-yl H Pentan-2-yl H 1a³⁸ SO₃H H H SO₃H 1a³⁹ SO₃H SO₃H H H Methyl Methyl CN 2- H 2- H 1a⁴⁰ SO₃H H H SO₃H Ethylhexyl Ethylhexyl 1a⁴¹ SO₃H SO₃H H H Methyl Methyl CN 2,2-Dimethyl H 2,2-Dimethyl propyl H 1a⁴² SO₃H H H SO₃H propyl 1a⁴³ SO₃H SO₃H H H Methyl Methyl CN Phenyl H Phenyl H 1a⁴⁴ SO₃H H H SO₃H 1a⁴⁵ SO₃H SO₃H H H Methyl Methyl CN Benzyl H Benzyl H 1a⁴⁶ SO₃H H H SO₃H 1a⁴⁷ SO₃H SO₃H H H Methyl Methyl CN Allyl H Allyl H 1a⁴⁸ SO₃H H H SO₃H 1a⁴⁹ SO₃H SO₃H H H Methyl Methyl CN 2-Methoxy H Butyl H 1a⁵⁰ SO₃H H H SO₃H ethyl 1a⁵¹ SO₃H SO₃H H H Methyl Methyl CN 3-Methoxy H 3-Methoxy propyl H 1a⁵² SO₃H H H SO₃H propyl 1a⁵³ SO₃H SO₃H H H Methyl Methyl CN 3-Methoxy H Butyl H 1a⁵⁴ SO₃H H H SO₃H propyl 1a⁵⁵ SO₃H SO₃H H H Methyl Methyl CN 2-Methyl H Sec-butyl H 1a⁵⁶ SO₃H H H SO₃H thioethyl 1a⁵⁷ SO₃H SO₃H H H Methyl Methyl CN 2-Methyl H 2-Hydroxyethyl H 1a⁵⁸ SO₃H H H SO₃H thioethyl 1a⁵⁹ SO₃H SO₃H H H Methyl Methyl CN Butyl Butyl 2-Hydroxyethyl H 1a⁶⁰ SO₃H H H SO₃H 1a⁶¹ SO₃H SO₃H H H Methyl Methyl CN Isopropyl Isopropyl 2-Hydroxyethyl H 1a⁶² SO₃H H H SO₃H 1a⁶³ SO₃H SO₃H H H Methyl Methyl CN 2-Fluoroethyl H Butyl H 1a⁶⁴ SO₃H H H SO₃H 1a⁶⁵ SO₃H SO₃H H H Methyl Methyl CN 2- H 2-Ethylhexyl H 1a⁶⁶ SO₃H H H SO₃H Chloroethyl 1a⁶⁷ SO₃H SO₃H H H Methyl Methyl CN 3-Chloro H 2-Ethylhexyl H 1a⁶⁸ SO₃H H H SO₃H propyl 1a⁶⁹ SO₃H SO₃H H H Methyl Methyl CN Tetrahydro H Butyl H 1a⁷⁰ SO₃H H H SO₃H furfuryl 1a⁷¹ SO₃H SO₃H H H Methyl Methyl CN 2-Furan-2-yl- H Butyl H 1a⁷² SO₃H H H SO₃H ethyl 1a⁷³ SO₃H SO₃H H H Methyl Methyl CN 2-(2-Hydroxy- H Butyl H 1a⁷⁴ SO₃H H H SO₃H ethyl sulfanyl)-ethyl 1a⁷⁵ SO₃H SO₃H H H Methyl Methyl CN 2-(2-tert-Butyl H Butyl H 1a⁷⁶ SO₃H H H SO₃H sulfanyl- ethane sulfonyl)-ethyl 1a⁷⁷ SO₃H SO₃H H H Methyl Methyl CN 2-Hydroxy- H Butyl H 1a⁷⁸ SO₃H H H SO₃H ethoxy propyl 1a⁷⁹ SO₃H SO₃H H H Methyl Methyl CN 2(2-hydroxy H Butyl H 1a⁸⁰ SO₃H H H SO₃H ethoxy)ethyl 1a⁸¹ SO₃H SO₃H H H Methyl Methyl CN H H 2-(2-Hydroxy ethoxy) H 1a⁸² SO₃H H H SO₃H propyl 1a⁸³ SO₃H SO₃H H H Methyl Methyl CN H H 2-(2-Hydroxy H 1a⁸⁴ SO₃H H H SO₃H ethoxy)ethyl 1a⁸⁵ SO₃H SO₃H H H Methyl Methyl CN H H 3-(4-Hydroxy H 1a⁸⁶ SO₃H H H SO₃H butoxy)propyl 1a⁸⁷ SO₃H SO₃H H H Methyl Methyl CN 2-(2-Hydroxy H H H 1a⁸⁸ SO₃H H H SO₃H ethoxy)ethyl 1a⁸⁹ SO₃H SO₃H H H Methyl Methyl CN 3-(4-Hydroxy H H H 1a⁹⁰ SO₃H H H SO₃H butoxy)propy 1a⁹¹ SO₃H SO₃H H H Methyl Methyl CN Phenyl H 2-(2-Hydroxy H 1a⁹² SO₃H H H SO₃H ethoxy)ethyl 1a⁹³ SO₃H SO₃H H H Methyl Methyl CN 3-(2- H H H 1a⁹⁴ SO₃H H H SO₃H Phenoxy ethoxy)- propyl 1a⁹⁵ SO₃H SO₃H H H Methyl Methyl CN 3- H 3-Isopropoxy-propyl H 1a⁹⁶ SO₃H H H SO₃H Isopropoxy- propyl 1a⁹⁷ SO₃H SO₃H H H Methyl Methyl CN 3- H H H 1a⁹⁸ SO₃H H H SO₃H Isopropoxy- propyl 1a⁹⁹ SO₃H SO₃H H H Methyl Methyl CN 3- H Phenyl H 1a¹⁰⁰ SO₃H H H SO₃H Isopropoxy- propyl 1a¹⁰¹ SO₃H SO₃H H H Methyl Methyl CN 3-Ethoxy- H 3-Ethoxy-propyl H 1a¹⁰² SO₃H H H SO₃H propyl 1a¹⁰³ SO₃H SO₃H H H Methyl Methyl CN 3-Ethoxy- H H H 1a¹⁰⁴ SO₃H H H SO₃H propyl 1a¹⁰⁵ SO₃H SO₃H H H Methyl Methyl CN 3-Ethoxy- H Phenyl H 1a¹⁰⁶ SO₃H H H SO₃H propyl 1a¹⁰⁷ SO₃H SO₃H H H Methyl Methyl CN 3- H 3-Ethoxybutyl H 1a¹⁰⁸ SO₃H H H SO₃H Ethoxybutyl 1a¹⁰⁹ SO₃H SO₃H H H Methyl Methyl CN 3- H H H 1a¹¹⁰ SO₃H H H SO₃H Ethoxybutyl 1a¹¹¹ SO₃H SO₃H H H Methyl Methyl CN 3- H Phenyl H 1a¹¹² SO₃H H H SO₃H Ethoxybutyl 1a¹¹³ SO₃H SO₃H H H Methyl Methyl CN 4-(2- H H H 1a¹¹⁴ SO₃H H H SO₃H Hydroxy- ethanesulfonyl)- phenyl 1a¹¹⁵ SO₃H SO₃H H H Methyl F CN 2-Methoxy H Butyl H 1a¹¹⁶ SO₃H H H SO₃H ethyl 1a¹¹⁷ SO₃H SO₃H H H Methyl F CN 3-Methoxy H Butyl H 1a¹¹⁸ SO₃H H H SO₃H propyl 1a¹¹⁹ SO₃H SO₃H H H Methyl F CN Butyl Butyl 2- H 1a¹²⁰ SO₃H H H SO₃H Hydroxyethyl 1a¹²¹ SO₃H SO₃H H H Methyl F CN Isopropyl Isopropyl 2- H 1a¹²² SO₃H H H SO₃H Hydroxyethyl 1a¹²³ SO₃H SO₃H H H Methyl F CN 2-Fluoro H Butyl H 1a¹²⁴ SO₃H H H SO₃H ethyl 1a¹²⁵ SO₃H SO₃H H H Methyl F CN 2-Chloro H 2- H 1a¹²⁶ SO₃H H H SO₃H ethyl Ethylhexyl 1a¹²⁷ SO₃H SO₃H H H Methyl F CN 3-Chloro H 2- H 1a¹²⁸ SO₃H H H SO₃H propyl Ethylhexyl 1a¹²⁹ SO₃H SO₃H H H Methyl F CN 2-(2- H Butyl H 1a¹³⁰ SO₃H H H SO₃H Hydroxy- ethyl sulfanyl)- ethyl 1a¹³¹ SO₃H SO₃H H H Methyl F CN 2-(2-tert- H Butyl H 1a¹³² SO₃H H H SO₃H Butyl sulfanyl- ethane sulfonyl)- ethyl 1a¹³³ SO₃H SO₃H H H Methyl F CN 2-Hydroxy H Butyl H 1a¹³⁴ SO₃H H H SO₃H ethoxy propyl 1a¹³⁵ SO₃H SO₃H H H Methyl F CN 2-Hydroxy H Butyl H 1a^(136\) SO₃H H H SO₃H ethoxyethyl 1a¹³⁷ SO₃H SO₃H H H Methyl F CN 2-(Ethyl sulfonyl) H Butyl H 1a¹³⁸ SO₃H H H SO₃H ethanol 1a¹³⁹ SO₃H SO₃H H H Methyl F CN H H 2-(2-Hydroxy H 1a¹⁴⁰ SO₃H H H SO₃H ethoxy) propyl 1a¹⁴¹ SO₃H SO₃H H H Methyl F CN H H 2-(2-Hydroxy H 1a¹⁴² SO₃H H H SO₃H ethoxy)ethyl 1a¹⁴³ SO₃H SO₃H H H Methyl F CN H H 3-(4-Hydroxy H 1a¹⁴⁴ SO₃H H H SO₃H butoxy)propyl 1a¹⁴⁵ SO₃H SO₃H H H Methyl F CN 2-(2-Hydroxy H H H 1a¹⁴⁶ SO₃H H H SO₃H ethoxy)ethyl 1a¹⁴⁷ SO₃H SO₃H H H Methyl F CN 3-(4-Hydroxy H H H 1a¹⁴⁸ SO₃H H H SO₃H butoxy)propyl 1a¹⁴⁹ SO₃H SO₃H H H Methyl F CN Phenyl H (2-Hydroxy H 1a¹⁵⁰ SO₃H H H SO₃H ethoxy)ethyl 1a¹⁵¹ SO₃H SO₃H H H Methyl F CN 3-(2-Phenoxy- H H H 1a¹⁵² SO₃H H H SO₃H ethoxy)-propyl 1a¹⁵³ SO₃H SO₃H H H Methyl F CN 3-Isopropoxy- H 3-Isopropoxy- H 1a¹⁵⁴ SO₃H H H SO₃H propyl propyl 1a¹⁵⁵ SO₃H SO₃H H H Methyl F CN 3-Isopropoxy- H H H 1a¹⁵⁶ SO₃H H H SO₃H propyl 1a¹⁵⁷ SO₃H SO₃H H H Methyl F CN 3-Isopropoxy- H Phenyl H 1a¹⁵⁸ SO₃H H H SO₃H propyl 1a¹⁵⁹ SO₃H SO₃H H H Methyl F CN 3-Ethoxy-propyl H 3-Ethoxy- H 1a¹⁶⁰ SO₃H H H SO₃H propyl 1a¹⁶¹ SO₃H SO₃H H H Methyl F CN 3-Ethoxy-propyl H H H 1a¹⁶² SO₃H H H SO₃H 1a¹⁶³ SO₃H SO₃H H H Methyl F CN 3-Ethoxy-propyl H Phenyl H 1a¹⁶⁴ SO₃H H H SO₃H 1a¹⁶⁵ SO₃H SO₃H H H Methyl F CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1a¹⁶⁶ SO₃H H H SO₃H 1a¹⁶⁷ SO₃H SO₃H H H Methyl F CN 3-Ethoxybutyl H H H 1a¹⁶⁸ SO₃H H H SO₃H 1a¹⁶⁹ SO₃H SO₃H H H Methyl F CN 3-Ethoxybutyl H Phenyl H 1a¹⁷⁰ SO₃H H H SO₃H 1a¹⁷¹ SO₃H SO₃H H H Methyl F CN 4-(2-Hydroxy- H H H 1a¹⁷² SO₃H H H SO₃H ethanesulfonyl)- phenyl 1a¹⁷³ SO₃H SO₃H H H NHCOCH₃ OMe CN 2-Methoxy ethyl H Butyl H 1a¹⁷⁴ SO₃H H H SO₃H 1a¹⁷⁵ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Methoxy H Butyl H 1a¹⁷⁶ SO₃H H H SO₃H propyl 1a¹⁷⁷ SO₃H H H SO₃H 1a¹⁷⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN Butyl Butyl 2-Hydroxyethyl H 1a¹⁷⁹ SO₃H H H SO₃H 1a¹⁸⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN Isopropyl Iso- 2-Hydroxyethyl H 1a¹⁸¹ SO₃H H H SO₃H propyl 1a¹⁸² SO₃H SO₃H H H NHCOCH₃ OMe CN 2-Fluoroethyl H Butyl H 1a¹⁸³ SO₃H H H SO₃H 1a¹⁸⁴ SO₃H SO₃H H H NHCOCH₃ OMe CN 2-Chloroethyl H 2-Ethylhexyl H 1a¹⁸⁵ SO₃H H H SO₃H 1a¹⁸⁶ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Chloropropyl H 2-Ethylhexyl H 1a¹⁸⁷ SO₃H H H SO₃H 1a¹⁸⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN 2-(2-Hydroxy- H Butyl H 1a¹⁸⁹ SO₃H H H SO₃H ethyl sulfanyl)- ethyl] 1a¹⁹⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN 2-(2-tert-Butyl H Butyl H 1a¹⁹¹ SO₃H H H SO₃H sulfanyl-ethane sulfonyl)-ethyl 1a¹⁹² SO₃H SO₃H H H NHCOCH₃ OMe CN 2- H Butyl H 1a¹⁹³ SO₃H H H SO₃H Hydroxyethoxy propyl 1a¹⁹⁴ SO₃H SO₃H H H NHCOCH₃ OMe CN 2-Hydroxy H Butyl H 1a¹⁹⁵ SO₃H H H SO₃H ethoxyethyl 1a¹⁹⁶ SO₃H SO₃H H H NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy) H 1a¹⁹⁷ SO₃H H H SO₃H propyl 1a¹⁹⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy)ethyl H 1a¹⁹⁹ SO₃H H H SO₃H 1a²⁰⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN H H 3-(4-Hydroxy H 1a²⁰¹ SO₃H H H SO₃H butoxy)propyl 1a²⁰² SO₃H SO₃H H H NHCOCH₃ OMe CN 2-(2-Hydroxy ethoxy)ethyl H H H 1a²⁰³ SO₃H H H SO₃H 1a²⁰⁴ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-(4-Hydroxy butoxy)propyl H H H 1a²⁰⁵ SO₃H H H SO₃H 1a²⁰⁶ SO₃H SO₃H H H NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy)ethyl H 1a²⁰⁷ SO₃H H H SO₃H 1a²⁰⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN Phenyl H 2-(2-Hydroxy ethoxy)ethyl H 1a²⁰⁹ SO₃H H H SO₃H 1a²¹⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H 1a²¹¹ SO₃H H H SO₃H propyl 1a²¹² SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1a²¹³ SO₃H H H SO₃H 1a²¹⁴ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1a²¹⁵ SO₃H H H SO₃H 1a²¹⁶ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1a²¹⁷ SO₃H H H SO₃H 1a²¹⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1a²¹⁹ SO₃H H H SO₃H 1a²²⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1a²²¹ SO₃H H H SO₃H 1a²²² SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1a²²³ SO₃H H H SO₃H 1a²²⁴ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1a²²⁵ SO₃H H H SO₃H 1a²²⁶ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxybutyl H H H 1a²²⁷ SO₃H H H SO₃H 1a²²⁸ SO₃H SO₃H H H NHCOCH₃ OMe CN 3-Ethoxybutyl H Phenyl H 1a²²⁹ SO₃H H H SO₃H 1a²³⁰ SO₃H SO₃H H H NHCOCH₃ OMe CN 4-(2-Hydroxy- H H H 1a²³¹ SO₃H H H SO₃H ethanesulfonyl)- phenyl 1a²³² SO₃H SO₃H H H Methyl Methyl CONH₂ Methyl H Methyl H 1a²³³ SO₃H H H SO₃H 1a²³⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ Ethyl H Ethyl H 1a²³⁵ SO₃H H H SO₃H 1a²³⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ Propyl H Propyl H 1a²³⁷ SO₃H H H SO₃H 1a²³⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ Butyl H Butyl H 1a²³⁹ SO₃H H H SO₃H 1a²⁴⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ Pentyl H Pentyl H 1a²⁴¹ SO₃H H H SO₃H 1a²⁴² SO₃H SO₃H H H Methyl Methyl CONH₂ Hexyl H Hexyl H 1a²⁴³ SO₃H H H SO₃H 1a²⁴⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ Cyclobutyl H Cyclobutyl H 1a²⁴⁵ SO₃H H H SO₃H 1a²⁴⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ Cyclopentyl H Cyclopentyl H 1a²⁴⁷ SO₃H H H SO₃H 1a²⁴⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ Cyclohexyl H Cyclohexyl H 1a²⁴⁹ SO₃H H H SO₃H 1a²⁵⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methyl cyclohexyl H 2-Methyl H 1a²⁵¹ SO₃H H H SO₃H cyclohexyl 1a²⁵² SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methyl cyclohexyl H 3-Methyl H 1a²⁵³ SO₃H H H SO₃H cyclohexyl 1a²⁵⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ Isopropyl H Isopropyl H 1a²⁵⁵ SO₃H H H SO₃H 1a²⁵⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ Sec-butyl H Sec-butyl H 1a²⁵⁷ SO₃H H H SO₃H 1a²⁵⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methylbutyl H 2-Methylbutyl H 1a²⁵⁹ SO₃H H H SO₃H 1a²⁶⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 1-Ethylpropyl H 1-Ethylpropyl H 1a²⁶¹ SO₃H H H SO₃H 1a²⁶² SO₃H SO₃H H H Methyl Methyl CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1a²⁶³ SO₃H H H SO₃H 1a²⁶⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ Tert-butyl H Tert-butyl H 1a²⁶⁵ SO₃H H H SO₃H 1a²⁶⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1a²⁶⁷ SO₃H H H SO₃H 1a²⁶⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ Pentan-2-yl H Pentan-2-yl H 1a²⁶⁹ SO₃H H H SO₃H 1a²⁷⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1a²⁷¹ SO₃H H H SO₃H 1a²⁷² SO₃H SO₃H H H Methyl Methyl CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1a²⁷³ SO₃H H H SO₃H 1a²⁷⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ Phenyl H Phenyl H 1a²⁷⁵ SO₃H H H SO₃H 1a²⁷⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ Benzyl H Benzyl H 1a²⁷⁷ SO₃H H H SO₃H 1a²⁷⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ Allyl H Allyl H 1a²⁷⁹ SO₃H H H SO₃H 1a²⁸⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methoxy ethyl H Butyl H 1a²⁸¹ SO₃H H H SO₃H 1a²⁸² SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1a²⁸³ SO₃H H H SO₃H 1a²⁸⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Methoxy propyl H Butyl H 1a²⁸⁵ SO₃H H H SO₃H 1a²⁸⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methyl thiothyl H Sec-butyl H 1a²⁸⁷ SO₃H H H SO₃H 1a²⁸⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Methyl thiothyl H 2-Hydroxyethyl H 1a²⁸⁹ SO₃H H H SO₃H 1a²⁹⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ Butyl Butyl 2-Hydroxyethyl H 1a²⁹¹ SO₃H H H SO₃H 1a²⁹² SO₃H SO₃H H H Methyl Methyl CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1a²⁹³ SO₃H H H SO₃H 1a²⁹⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Fluoroethyl H Butyl H 1a²⁹⁵ SO₃H H H SO₃H 1a²⁹⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Chloroethyl H 2-Ethylhexyl H 1a²⁹⁷ SO₃H H H SO₃H 1a²⁹⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Chloro propyl H 2-Ethylhexyl H 1a²⁹⁹ SO₃H H H SO₃H 1a³⁰⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ Tetrahydro H Butyl H 1a³⁰¹ SO₃H H H SO₃H furfuryl 1a³⁰² SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Furan-2-yl- H Butyl H 1a³⁰³ SO₃H H H SO₃H ethyl 1a³⁰⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-(2-Hydroxy- H Butyl H 1a³⁰⁵ SO₃H H H SO₃H ethyl sulfanyl)- ethyl 1a³⁰⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-(2-tert-Butyl H Butyl H 1a³⁰⁷ SO₃H H H SO₃H sulfanyl-ethane sylfonyl)-ethyl 1a³⁰⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 2- H Butyl H 1a³⁰⁹ SO₃H H H SO₃H Hydroxyethoxy propyl 1a³¹⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-Hydroxy H Butyl H 1a³¹¹ SO₃H H H SO₃H ethoxyethyl 1a³¹² SO₃H SO₃H H H Methyl Methyl CONH₂ H H 2-(2-Hydroxy ethoxy) H 1a³¹³ SO₃H H H SO₃H propyl 1a³¹⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ H H 2-(2-Hydroxy ethoxy)ethyl H 1a³¹⁵ SO₃H H H SO₃H 1a³¹⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ H H 3-(4-Hydroxy H 1a³¹⁷ SO₃H H H SO₃H butoxy)propyl 1a³¹⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 2-(2-Hydroxy H H H 1a³¹⁹ SO₃H H H SO₃H ethoxy)ethyl 1a³²⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-(4-Hydroxy H H H 1a³²¹ SO₃H H H SO₃H butoxy)propyl 1a³²² SO₃H SO₃H H H Methyl Methyl CONH₂ Phenyl H 2-(2-Hydroxy ethoxy)ethyl H 1a³²³ SO₃H H H SO₃H 1a³²⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-(2-Phenoxy-ethoxy)- H H H 1a³²⁵ SO₃H H H SO₃H propyl 1a³²⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1a³²⁷ SO₃H H H SO₃H 1a³²⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Isopropoxy-propyl H H H 1a³²⁹ SO₃H H H SO₃H 1a³³⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Isopropoxy-propyl H Phenyl H 1a³³¹ SO₃H H H SO₃H 1a³³² SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1a³³³ SO₃H H H SO₃H 1a³³⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxy-propyl H H H 1a³³⁵ SO₃H H H SO₃H 1a³³⁶ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxy-propyl H Phenyl H 1a³³⁷ SO₃H H H SO₃H 1a³³⁸ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxybutyl H 3-Ethoxybutyl H 1a³³⁹ SO₃H H H SO₃H 1a³⁴⁰ SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxybutyl H H H 1a³⁴¹ SO₃H H H SO₃H 1a³⁴² SO₃H SO₃H H H Methyl Methyl CONH₂ 3-Ethoxybutyl H Phenyl H 1a³⁴³ SO₃H H H SO₃H 1a³⁴⁴ SO₃H SO₃H H H Methyl Methyl CONH₂ 4-(2-Hydroxy- H H H 1a³⁴⁵ SO₃H H H SO₃H ethanesulfonyl)-phenyl 1a³⁴⁶ SO₃H SO₃H H H Methyl F CONH₂ 2-Methoxy ethyl H Butyl H 1a³⁴⁷ SO₃H H H SO₃H 1a³⁴⁸ SO₃H SO₃H H H Methyl F CONH₂ 2-Methoxy propyl H Butyl H 1a³⁴⁹ SO₃H H H SO₃H 1a³⁵⁰ SO₃H SO₃H H H Methyl F CONH₂ Butyl Butyl 2-Hydroxyethyl H 1a³⁵¹ SO₃H H H SO₃H 1a³⁵² SO₃H SO₃H H H Methyl F CONH₂ Isopropyl Iso-propyl 2-Hydrox-yethyl H 1a³⁵³ SO₃H H H SO₃H 1a³⁵⁴ SO₃H SO₃H H H Methyl F CONH₂ 2-Fluoro ethyl H Butyl H 1a³⁵⁵ SO₃H H H SO₃H 1a³⁵⁶ SO₃H SO₃H H H Methyl F CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1a³⁵⁷ SO₃H H H SO₃H 1a³⁵⁸ SO₃H SO₃H H H Methyl F CONH₂ 3-Chloro propyl H 2-Ethylhexyl H 1a³⁵⁹ SO₃H H H SO₃H 1a³⁶⁰ SO₃H SO₃H H H Methyl F CONH₂ 2-(2-Hydroxy-ethyl H Butyl H 1a³⁶¹ SO₃H H H SO₃H sulfanyl)-ethyl 1a³⁶² SO₃H SO₃H H H Methyl F CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H 1a³⁶³ SO₃H H H SO₃H ethane sulfonyl)-ethyl 1a³⁶⁴ SO₃H SO₃H H H Methyl F CONH₂ 2-Hydroxy ethoxy H Butyl H 1a³⁶⁵ SO₃H H H SO₃H propyl 1a³⁶⁶ SO₃H SO₃H H H Methyl F CONH₂ 2-Hydroxy ethoxyethyl H Butyl H 1a³⁶⁷ SO₃H H H SO₃H 1a³⁶⁸ SO₃H SO₃H H H Methyl F CONH₂ 2-(Ethyl sulfonyl) ethanol H Butyl H 1a³⁶⁹ SO₃H H H SO₃H 1a³⁷⁰ SO₃H SO₃H H H Methyl F CONH₂ H H 2-(2-Hydroxy ethoxy) H 1a³⁷¹ SO₃H H H SO₃H propyl 1a³⁷² SO₃H SO₃H H H Methyl F CONH₂ H H 2-(2-Hydroxy H 1a³⁷³ SO₃H H H SO₃H ethoxy)ethyl 1a³⁷⁴ SO₃H SO₃H H H Methyl F CONH₂ H H 3-(4-Hydroxy H 1a³⁷⁵ SO₃H H H SO₃H butoxy)propyl 1a³⁷⁶ SO₃H SO₃H H H Methyl F CONH₂ 2-(2-Hydroxy H H H 1a³⁷⁷ SO₃H H H SO₃H ethoxy)ethyl 1a³⁷⁸ SO₃H SO₃H H H Methyl F CONH₂ 3-(4-Hydroxy H H H 1a³⁷⁹ SO₃H H H SO₃H butoxy)propyl 1a³⁸⁰ SO₃H SO₃H H H Methyl F CONH₂ Phenyl H (2-Hydroxy ethoxy)ethyl H 1a³⁸¹ SO₃H H H SO₃H 1a³⁸² SO₃H SO₃H H H Methyl F CONH₂ 3-(2-Phenoxy-ethoxy)- H H H 1a³⁸³ SO₃H H H SO₃H propyl 1a³⁸⁴ SO₃H SO₃H H H Methyl F CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1a³⁸⁵ SO₃H H H SO₃H 1a³⁸⁶ SO₃H SO₃H H H Methyl F CONH₂ 3-Isopropoxy-propyl H H H 1a³⁸⁷ SO₃H H H SO₃H 1a³⁸⁸ SO₃H SO₃H H H Methyl F CONH₂ 3-Isopropoxy-propyl H Phenyl H 1a³⁸⁹ SO₃H H H SO₃H 1a³⁹⁰ SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxy-propyl H 3-Ethoxy- H 1a³⁹¹ SO₃H H H SO₃H propyl 1a³⁹² SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxy-propyl H H H 1a³⁹³ SO₃H H H SO₃H 1a³⁹⁴ SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxy-propyl H Phenyl H 1a³⁹⁵ SO₃H H H SO₃H 1a³⁹⁶ SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxybutyl H 3- H 1a³⁹⁷ SO₃H H H SO₃H Ethoxybutyl 1a³⁹⁸ SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxybutyl H H H 1a³⁹⁹ SO₃H H H SO₃H 1a⁴⁰⁰ SO₃H SO₃H H H Methyl F CONH₂ 3-Ethoxybutyl H Phenyl H 1a⁴⁰¹ SO₃H H H SO₃H 1a⁴⁰² SO₃H SO₃H H H Methyl F CONH₂ 4-(2-Hydroxy- H H H 1a⁴⁰³ SO₃H H H SO₃H ethanesulfonyl)- phenyl 1a⁴⁰⁴ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-Methoxy H Butyl H 1a⁴⁰⁵ SO₃H H H SO₃H ethyl 1a⁴⁰⁶ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Methoxy H Butyl H 1a⁴⁰⁷ SO₃H H H SO₃H propyl 1a⁴⁰⁸ SO₃H H H SO₃H 1a⁴⁰⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ Butyl Butyl 2- H 1a⁴¹⁰ SO₃H H H SO₃H Hydroxyethyl 1a⁴¹¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ Isopropyl Iso- 2- H 1a⁴¹² SO₃H H H SO₃H propyl Hydroxyethyl 1a⁴¹³ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-Fluoroethyl H Butyl H 1a⁴¹⁴ SO₃H H H SO₃H 1a⁴¹⁵ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-Chloroethyl H 2-Ethylhexyl H 1a⁴¹⁶ SO₃H H H SO₃H 1a⁴¹⁷ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Chloropropyl H 2-Ethylhexyl H 1a⁴¹⁸ SO₃H H H SO₃H 1a⁴¹⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-(2-Hydroxy- H Butyl H 1a⁴²⁰ SO₃H H H SO₃H ethyl sulfanyl)- ethyl] 1a⁴²¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl H Butyl H 1a⁴²² SO₃H H H SO₃H sulfanyl-ethane sulfonyl)-ethyl 1a⁴²³ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2- H Butyl H 1a⁴²⁴ SO₃H H H SO₃H Hydroxyethoxy propyl 1a⁴²⁵ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-Hydroxy H Butyl H 1a⁴²⁶ SO₃H H H SO₃H ethoxyethyl 1a⁴²⁷ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy ethoxy) H 1a⁴²⁸ SO₃H H H SO₃H propyl 1a⁴²⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy H 1a⁴³⁰ SO₃H H H SO₃H ethoxy)ethyl 1a⁴³¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ H H 3-(4-Hydroxy H 1a⁴³² SO₃H H H SO₃H butoxy)propyl 1a⁴³³ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 2-(2-Hydroxy ethoxy)ethyl H H H 1a⁴³⁴ SO₃H H H SO₃H 1a⁴³⁵ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-(4-Hydroxy butoxy)- H H H 1a⁴³⁶ SO₃H H H SO₃H propyl 1a⁴³⁷ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy- H 1a⁴³⁸ SO₃H H H SO₃H ethoxy)ethyl 1a⁴³⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy- H 1a⁴⁴⁰ SO₃H H H SO₃H ethoxy)ethyl 1a⁴⁴¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H 1a⁴⁴² SO₃H H H SO₃H propyl 1a⁴⁴³ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1a⁴⁴⁴ SO₃H H H SO₃H 1a⁴⁴⁵ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1a⁴⁴⁶ SO₃H H H SO₃H 1a⁴⁴⁷ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Isopropoxy- H Phenyl H 1a⁴⁴⁸ SO₃H H H SO₃H propyl 1a⁴⁴⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy- H 1a⁴⁵⁰ SO₃H H H SO₃H propyl 1a⁴⁵¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1a⁴⁵² SO₃H H H SO₃H 1a⁴⁵³ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1a⁴⁵⁴ SO₃H H H SO₃H 1a⁴⁵⁵ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H 3- H 1a⁴⁵⁶ SO₃H H H SO₃H Ethoxybutyl 1a⁴⁵⁷ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H H H 1a⁴⁵⁸ SO₃H H H SO₃H 1a⁴⁵⁹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H Phenyl H 1a⁴⁶⁰ SO₃H H H SO₃H 1a⁴⁶¹ SO₃H SO₃H H H NHCOCH₃ OMe CONH₂ 4-(2-hydroxy- H H H 1a⁴⁶² SO₃H H H SO₃H ethanesulfonyl)- phenyl

Further particularly preferred embodiments of the present invention are dyes of formula (1b) and mixtures thereof

wherein R^(1b), R^(2b), R^(3b) and R^(4b) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5b), R^(6b), R^(7b) and R^(8b) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9b) and R^(15b) independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10b) and R^(16b) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstiuted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl, R^(11b), R^(12b) R^(13b), R^(14b), R^(17b), R^(18b), R^(19b) and R^(20b) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyi-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyi-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsuifonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In particularly preferred dyes of formula (1b):

R^(3b) and R^(4b) is SO₃M, R^(1b) and R^(2b) is hydrogen, R^(5b), R^(6b), R^(7b) and R^(8b) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9b) and R^(15b) independent of each other is cyano or carbamoyl, R^(1b) and R^(16b) is methyl, R^(11b), R^(12b) R^(13b), R^(14b), R^(17b), R^(18b), R^(19b) and R^(20b) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of such particularly preferred dyes of formula (1b) are the compounds of formulae (1b¹ to 1b³⁶⁴) and mixtures thereof:

Structure R^(5b)/R^(7b) R^(6b)/R^(8b) R^(9b)/R^(16b) R^(11b)/R^(17b) R^(12b)/R^(18b) R^(13b)/R^(19b) R^(14b)/R^(20b) 1b¹ Methyl Methyl CN Methyl H Methyl H 1b² Methyl Methyl CN Ethyl H Ethyl H 1b³ Methyl Methyl CN Propyl H Propyl H 1b⁴ Methyl Methyl CN Butyl H Butyl H 1b⁵ Methyl Methyl CN Pentyl H Pentyl H 1b⁶ Methyl Methyl CN Hexyl H Hexyl H 1b⁷ Methyl Methyl CN Cyclobutyl H Cyclobutyl H 1b⁸ Methyl Methyl CN Cyclopentyl H Cyclopentyl H 1b⁹ Methyl Methyl CN Cyclohexyl H Cyclohexyl H 1b¹⁰ Methyl Methyl CN 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1b¹¹ Methyl Methyl CN 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1b¹² Methyl Methyl CN Isopropyl H Isopropyl H 1b¹³ Methyl Methyl CN Sec-butyl H Sec-butyl H 1b¹⁴ Methyl Methyl CN 2-Methylbutyl H 2-Methylbutyl H 1b¹⁵ Methyl Methyl CN 1-Ethylpropyl H 1-Ethylpropyl H 1b¹⁶ Methyl Methyl CN 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1b¹⁷ Methyl Methyl CN Tert-butyl H Tert-butyl H 1b¹⁸ Methyl Methyl CN 3-Methylbutyl H 3-Methylbutyl H 1b¹⁹ Methyl Methyl CN Pentan-2-yl H Pentan-2-yl H 1b²⁰ Methyl Methyl CN 2-Ethylhexyl H 2-Ethylhexyl H 1b²¹ Methyl Methyl CN 2,2-Dimethylpropyl H 2,2-Dimethylpropyl H 1b²² Methyl Methyl CN Phenyl H Phenyl H 1b²³ Methyl Methyl CN Benzyl H Benzyl H 1b²⁴ Methyl Methyl CONH₂ Methyl H Methyl H 1b²⁵ Methyl Methyl CONH₂ Ethyl H Ethyl H 1b²⁶ Methyl Methyl CONH₂ Propyl H Propyl H 1b²⁷ Methyl Methyl CONH₂ Butyl H Butyl H 1b²⁸ Methyl Methyl CONH₂ Pentyl H Pentyl H 1b²⁹ Methyl Methyl CONH₂ Hexyl H Hexyl H 1b³⁰ Methyl Methyl CONH₂ Cyclobutyl H Cyclobutyl H 1b³¹ Methyl Methyl CONH₂ Cyclopentyl H Cyclopentyl H 1b³² Methyl Methyl CONH₂ Cyclohexyl H Cyclohexyl H 1b³³ Methyl Methyl CONH₂ 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1b³⁴ Methyl Methyl CONH₂ 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1b³⁵ Methyl Methyl CONH₂ Isopropyl H Isopropyl H 1b³⁶ Methyl Methyl CONH₂ Sec-butyl H Sec-butyl H 1b³⁷ Methyl Methyl CONH₂ 2-Methylbutyl H 2-Methylbutyl H 1b³⁸ Methyl Methyl CONH₂ 1-Ethylpropyl H 1-Ethylpropyl H 1b³⁹ Methyl Methyl CONH₂ 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1b⁴⁰ Methyl Methyl CONH₂ Tert-butyl H Tert-butyl H 1b⁴¹ Methyl Methyl CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1b⁴² Methyl Methyl CONH₂ Pentan-2-yl H Pentan-2-yl H 1b⁴³ Methyl Methyl CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1b⁴⁴ Methyl Methyl CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1b⁴⁵ Methyl Methyl CONH₂ Phenyl H Phenyl H 1b⁴⁶ Methyl Methyl CONH₂ Benzyl H Benzyl H 1b⁴⁷ Methyl F CN Methyl H Methyl H 1b⁴⁸ Methyl F CN Ethyl H Ethyl H 1b⁴⁹ Methyl F CN Propyl H Propyl H 1b⁵⁰ Methyl F CN Butyl H Butyl H 1b⁵¹ Methyl F CN Pentyl H Pentyl H 1b⁵² Methyl F CN Hexyl H Hexyl H 1b⁵³ Methyl F CN Cyclobutyl H Cyclobutyl H 1b⁵⁴ Methyl F CN Cyclopentyl H Cyclopentyl H 1b⁵⁵ Methyl F CN Cyclohexyl H Cyclohexyl H 1b⁵⁶ Methyl F CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1b⁵⁷ Methyl F CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1b⁵⁸ Methyl F CN Isopropyl H Isopropyl H 1b⁵⁹ Methyl F CN Sec-butyl H Sec-butyl H 1b⁶⁰ Methyl F CN 2-Methyl butyl H 2-Methyl H butyl 1b⁶¹ Methyl F CN 1-Ethyl propyl H 1-Ethyl propyl H 1b⁶² Methyl F CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1b⁶³ Methyl F CN Tert-butyl H Tert-butyl H 1b⁶⁴ Methyl F CN 3-Methyl butyl H 3-Methyl butyl H 1b⁶⁵ Methyl F CN Pentan-2-yl H Pentan-2-yl H 1b⁶⁶ Methyl F CN 2-Ethylhexyl H 2-Ethylhexyl H 1b⁶⁷ Methyl F CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1b⁶⁸ Methyl F CN Phenyl H Phenyl H 1b⁶⁹ Methyl F CN Benzyl H Benzyl H 1b⁷⁰ Methyl F CONH₂ Methyl H Methyl H 1b⁷¹ Methyl F CONH₂ Ethyl H Ethyl H 1b⁷² Methyl F CONH₂ Propyl H Propyl H 1b⁷³ Methyl F CONH₂ Butyl H Butyl H 1b⁷⁴ Methyl F CONH₂ Pentyl H Pentyl H 1b⁷⁵ Methyl F CONH₂ Hexyl H Hexyl H 1b⁷⁶ Methyl F CONH₂ Cyclobutyl H Cyclobutyl H 1b⁷⁷ Methyl F CONH₂ Cyclopentyl H Cyclopentyl H 1b⁷⁸ Methyl F CONH₂ Cyclohexyl H Cyclohexyl H 1b⁷⁹ Methyl F CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1b⁸⁰ Methyl F CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1b⁸¹ Methyl F CONH₂ Isopropyl H Isopropyl H 1b⁸² Methyl F CONH₂ Sec-butyl H Sec-butyl H 1b⁸³ Methyl F CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1b⁸⁴ Methyl F CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1b⁸⁵ Methyl F CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1b⁸⁶ Methyl F CONH₂ Tert-butyl H Tert-butyl H 1b⁸⁷ Methyl F CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1b⁸⁸ Methyl F CONH₂ Pentan-2-yl H Pentan-2-yl H 1b⁸⁹ Methyl F CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1b⁹⁰ Methyl F CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1b⁹¹ Methyl F CONH₂ Phenyl H Phenyl H 1b⁹² Methyl F CONH₂ Benzyl H Benzyl H 1b⁹³ NHCOCH₃ OMe CN Methyl H Methyl H 1b⁹⁴ NHCOCH₃ OMe CN Ethyl H Ethyl H 1b⁹⁵ NHCOCH₃ OMe CN Propyl H Propyl H 1b⁹⁶ NHCOCH₃ OMe CN Butyl H Butyl H 1b⁹⁷ NHCOCH₃ OMe CN Pentyl H Pentyl H 1b⁹⁸ NHCOCH₃ OMe CN Hexyl H Hexyl H 1b⁹⁹ NHCOCH₃ OMe CN Cyclobutyl H Cyclobutyl H 1b¹⁰⁰ NHCOCH₃ OMe CN Cyclopentyl H Cyclopentyl H 1b¹⁰¹ NHCOCH₃ OMe CN Cyclohexyl H Cyclohexyl H 1b¹⁰² NHCOCH₃ OMe CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1b¹⁰³ NHCOCH₃ OMe CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1b¹⁰⁴ NHCOCH₃ OMe CN Isopropyl H Isopropyl H 1b¹⁰⁵ NHCOCH₃ OMe CN Sec-butyl H Sec-butyl H 1b¹⁰⁶ NHCOCH₃ OMe CN 2-Methyl butyl H 2-Methyl H butyl 1b¹⁰⁷ NHCOCH₃ OMe CN 1-Ethyl propyl H 1-Ethyl propyl H 1b¹⁰⁸ NHCOCH₃ OMe CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1b¹⁰⁹ NHCOCH₃ OMe CN Tert-butyl H Tert-butyl H 1b¹¹⁰ NHCOCH₃ OMe CN 3-Methyl butyl H 3-Methyl butyl H 1b¹¹¹ NHCOCH₃ OMe CN Pentan-2-yl H Pentan-2-yl H 1b¹¹² NHCOCH₃ OMe CN 2-Ethylhexyl H 2-Ethylhexyl H 1b¹¹³ NHCOCH₃ OMe CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1b¹¹⁴ NHCOCH₃ OMe CN Phenyl H Phenyl H 1b¹¹⁵ NHCOCH₃ OMe CN Benzyl H Benzyl H 1b¹¹⁶ NHCOCH₃ OMe CONH₂ Methyl H Methyl H 1b¹¹⁷ NHCOCH₃ OMe CONH₂ Ethyl H Ethyl H 1b¹¹⁸ NHCOCH₃ OMe CONH₂ Propyl H Propyl H 1b¹¹⁹ NHCOCH₃ OMe CONH₂ Butyl H Butyl H 1b¹²⁰ NHCOCH₃ OMe CONH₂ Pentyl H Pentyl H 1b¹²¹ NHCOCH₃ OMe CONH₂ Hexyl H Hexyl H 1b¹²² NHCOCH₃ OMe CONH₂ Cyclobutyl H Cyclobutyl H 1b¹²³ NHCOCH₃ OMe CONH₂ Cyclopentyl H Cyclopentyl H 1b¹²⁴ NHCOCH₃ OMe CONH₂ Cyclohexyl H Cyclohexyl H 1b¹²⁵ NHCOCH₃ OMe CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1b¹²⁶ NHCOCH₃ OMe CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1b¹²⁷ NHCOCH₃ OMe CONH₂ Isopropyl H Isopropyl H 1b¹²⁸ NHCOCH₃ OMe CONH₂ Sec-butyl H Sec-butyl H 1b¹²⁹ NHCOCH₃ OMe CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1b¹³⁰ NHCOCH₃ OMe CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1b¹³¹ NHCOCH₃ OMe CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1b¹³² NHCOCH₃ OMe CONH₂ Tert-butyl H Tert-butyl H 1b¹³³ NHCOCH₃ OMe CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1b¹³⁴ NHCOCH₃ OMe CONH₂ Pentan-2-yl H Pentan-2-yl H 1b¹³⁵ NHCOCH₃ OMe CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1b¹³⁶ NHCOCH₃ OMe CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1b¹³⁷ NHCOCH₃ OMe CONH₂ Phenyl H Phenyl H 1b¹³⁸ NHCOCH₃ OMe CONH₂ Benzyl H Benzyl H 1b¹³⁹ Methyl Methyl CN 2-Methoxyethyl H Butyl H 1b¹⁴⁰ Methyl Methyl CN 3-Methoxy propyl H 3-Methoxy propyl H 1b¹⁴¹ Methyl Methyl CN 3-Methoxy propyl H Butyl H 1b¹⁴² Methyl Methyl CN Butyl Butyl 2-Hydroxyethyl H 1b¹⁴³ Methyl Methyl CN Isopropyl Isopropyl 2-Hydroxyethyl H 1b¹⁴⁴ Methyl Methyl CN 2-Fluoro ethyl H Butyl H 1b¹⁴⁵ Methyl Methyl CN 2-Chloro ethyl H 2-Ethylhexyl H 1b¹⁴⁶ Methyl Methyl CN 3-Chloro propyl H 2-Ethylhexyl H 1b¹⁴⁷ Methyl Methyl CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b¹⁴⁸ Methyl Methyl CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b¹⁴⁹ Methyl Methyl CN 2-(2-Hydroxy ethoxy) H Butyl H propyl 1b¹⁵⁰ Methyl Methyl CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b¹⁵¹ Methyl Methyl CN H H 2-(2-Hydroxy ethoxy) H propyl 1b¹⁵² Methyl Methyl CN H H 2-(2-Hydroxy H ethoxy)ethyl 1b¹⁵³ Methyl Methyl CN H H 3-(2-Hydroxy H ethoxy)propyl 1b¹⁵⁴ Methyl Methyl CN 2-(2-Hydroxy H H H ethoxy)ethyl 1b¹⁵⁵ Methyl Methyl CN 3-(2-Hydroxy H H H ethoxy)propyl 1b¹⁵⁶ Methyl Methyl CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b¹⁵⁷ Methyl Methyl CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1b¹⁵⁸ Methyl Methyl CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b¹⁵⁹ Methyl Methyl CN 3-Isopropoxy-propyl H H H 1b¹⁶⁰ Methyl Methyl CN 3-Isopropoxy-propyl H Phenyl H 1b¹⁶¹ Methyl Methyl CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b¹⁶² Methyl Methyl CN 3-Ethoxy-propyl H H H 1b¹⁶³ Methyl Methyl CN 3-Ethoxy-propyl H Phenyl H 1b¹⁶⁴ Methyl Methyl CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1b¹⁶⁵ Methyl Methyl CN 3-Ethoxybutyl H H H 1b¹⁶⁶ Methyl Methyl CN 3-Ethoxybutyl H Phenyl H 1b¹⁶⁷ Methyl Methyl CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1b¹⁶⁸ Methyl F CN 2-Methoxyethyl H Butyl H 1b¹⁶⁹ Methyl F CN 3-Methoxy propyl H 3-Methoxy propyl H 1b¹⁷⁰ Methyl F CN 3-Methoxy propyl H Butyl H 1b¹⁷¹ Methyl F CN Butyl Butyl 2-Hydroxyethyl H 1b¹⁷² Methyl F CN Isopropyl Isopropyl 2-Hydroxyethyl H 1b¹⁷³ Methyl F CN 2-Fluoro ethyl H Butyl H 1b¹⁷⁴ Methyl F CN 2-Chloro ethyl H 2-Ethylhexyl H 1b¹⁷⁵ Methyl F CN 3-Chloro propyl H 2-Ethylhexyl H 1b¹⁷⁶ Methyl F CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b¹⁷⁷ Methyl F CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b¹⁷⁸ Methyl F CN 2-Hydroxy ethoxy H Butyl H propyl 1b¹⁷⁹ Methyl F CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b¹⁸⁰ Methyl F CN H H 2-(2-Hydroxy ethoxy) H propyl 1b¹⁸¹ Methyl F CN H H 2-(2-Hydroxy H ethoxy)ethyl 1b¹⁸² Methyl F CN H H 3-(4-Hydroxy H ethoxy)propyl 1b¹⁸³ Methyl F CN 2-(2-Hydroxy H H H ethoxy)ethyl 1b¹⁸⁴ Methyl F CN 3-(4-Hydroxy H H H ethoxy)propyl 1b¹⁸⁵ Methyl F CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b¹⁸⁶ Methyl F CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1b¹⁸⁷ Methyl F CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b¹⁸⁸ Methyl F CN 3-Isopropoxy-propyl H H H 1b¹⁸⁹ Methyl F CN 3-Isopropoxy-propyl H Phenyl H 1b¹⁹⁰ Methyl F CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b¹⁹¹ Methyl F CN 3-Ethoxy-propyl H H 1b¹⁹² Methyl F CN 3-Ethoxy-propyl H Phenyl H 1b¹⁹³ Methyl F CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1b¹⁹⁴ Methyl F CN 3-Ethoxybutyl H H 1b¹⁹⁵ Methyl F CN 3-Ethoxybutyl H Phenyl H 1b¹⁹⁶ Methyl F CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1b¹⁹⁷ NHCOCH₃ OMe CN 2-Methoxyethyl H Butyl H 1b¹⁹⁸ NHCOCH₃ OMe CN 3-Methoxy propyl H 3-Methoxy propyl H 1b¹⁹⁹ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1b²⁰⁰ NHCOCH₃ OMe CN Butyl Butyl 2-Hydroxyethyl H 1b²⁰¹ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxyethyl H 1b²⁰² NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1b²⁰³ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethylhexyl H 1b²⁰⁴ NHCOCH₃ OMe CN 3-Chloro propyl H 2-Ethylhexyl H 1b²⁰⁵ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b²⁰⁶ NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b²⁰⁷ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1b²⁰⁸ NHCOCH₃ OMe CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b²⁰⁹ NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy) H propyl 1b²¹⁰ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1b²¹¹ NHCOCH₃ OMe CN H H 3-(4-Hydroxy H ethoxy)propyl 1b²¹² NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1b²¹³ NHCOCH₃ OMe CN 3-(4-Hydroxy H H H ethoxy)propyl 1b²¹⁴ NHCOCH₃ OMe CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b²¹⁵ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1b²¹⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b²¹⁷ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1b²¹⁸ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1b²¹⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b²²⁰ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1b²²¹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1b²²² NHCOCH₃ OMe CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1b²²³ NHCOCH₃ OMe CN 3-Ethoxybutyl H H H 1b²²⁴ NHCOCH₃ OMe CN 3-Ethoxybutyl H Phenyl H 1b²²⁵ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1b²²⁶ NHCOCH₃ OMe CN Butyl 2-Hydroxyethyl H 1b²²⁷ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxyethyl H 1b²²⁸ NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1b²²⁹ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethylhexyl H 1b²³⁰ NHCOCH₃ OMe CN 3-Chloro propyl H 2-Ethylhexyl H 1b²³¹ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b²³² NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b²³³ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1b²³⁴ NHCOCH₃ OMe CN 2-Hydroxy ethoxyethyl H Butyl H 1b²³⁵ NHCOCH₃ OMe CN 2-(Ethyl sulfonyl) ethanol H Butyl H 1b²³⁶ NHCOCH₃ OMe CN H H (2-Hydroxy ethoxy) H propyl 1b²³⁷ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1b²³⁸ NHCOCH₃ OMe CN H H 3-(2-Hydroxy H ethoxy)propyl 1b²³⁹ NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1b²⁴⁰ NHCOCH₃ OMe CN 3-(4-Hydroxy H H H ethoxy)propyl 1b²⁴¹ NHCOCH₃ OMe CN H H (2-Hydroxy H ethoxy)ethyl 1b²⁴² NHCOCH₃ OMe CN Phenyl H (2-Hydroxy H ethoxy)ethyl 1b²⁴³ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1b²⁴⁴ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b²⁴⁵ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1b²⁴⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1b²⁴⁷ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b²⁴⁸ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1b²⁴⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1b²⁵⁰ NHCOCH₃ OMe CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1b²⁵¹ NHCOCH₃ OMe CN 3-Ethoxybutyl H H H 1b²⁵² NHCOCH₃ OMe CN 3-Ethoxybutyl H Phenyl H 1b²⁵³ NHCOCH₃ OMe CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1b²⁵⁴ Methyl Methyl CONH₂ 2-Methoxyethyl H Butyl H 1b²⁵⁵ Methyl Methyl CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1b²⁵⁶ Methyl Methyl CONH₂ 3-Methoxy propyl H Butyl H 1b²⁵⁷ Methyl Methyl CONH₂ Butyl Butyl 2-Hydroxyethyl H 1b²⁵⁸ Methyl Methyl CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1b²⁵⁹ Methyl Methyl CONH₂ 2-Fluoro ethyl H Butyl H 1b²⁶⁰ Methyl Methyl CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1b²⁶¹ Methyl Methyl CONH₂ 3-Chloro propyl H 2-Ethylhexyl H 1b²⁶² Methyl Methyl CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b²⁶³ Methyl Methyl CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b²⁶⁴ Methyl Methyl CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1b²⁶⁵ Methyl Methyl CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b²⁶⁶ Methyl Methyl CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1b²⁶⁷ Methyl Methyl CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1b²⁶⁸ Methyl Methyl CONH₂ H H 3-(4-Hydroxy H ethoxy)propyl 1b²⁶⁹ Methyl Methyl CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1b²⁷⁰ Methyl Methyl CONH₂ 3-(4-Hydroxy H H H ethoxy)propyl 1b²⁷¹ Methyl Methyl CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b²⁷² Methyl Methyl CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1b²⁷³ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b²⁷⁴ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H H H 1b²⁷⁵ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H Phenyl H 1b²⁷⁶ Methyl Methyl CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b²⁷⁷ Methyl Methyl CONH₂ 3-Ethoxy-propyl H H H 1b²⁷⁸ Methyl Methyl CONH₂ 3-Ethoxy-propyl H Phenyl H 1b²⁷⁹ Methyl Methyl CONH₂ 3-Ethoxybutyl H 3-Ethoxy butyl H 1b²⁸⁰ Methyl Methyl CONH₂ 3-Ethoxybutyl H H H 1b²⁸¹ Methyl Methyl CONH₂ 3-Ethoxybutyl H Phenyl H 1b²⁸² Methyl Methyl CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1b²⁸³ Methyl F CONH₂ 2-Methoxyethyl H Butyl H 1b²⁸⁴ Methyl F CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1b²⁸⁵ Methyl F CONH₂ 3-Methoxy propyl H Butyl H 1b²⁸⁶ Methyl F CONH₂ Butyl Butyl 2-Hydroxyethyl H 1b²⁸⁷ Methyl F CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1b²⁸⁸ Methyl F CONH₂ 2-Fluoro ethyl H Butyl H 1b²⁸⁹ Methyl F CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1b²⁹⁰ Methyl F CONH₂ 2-Chloro propyl H 2-Ethylhexyl H 1b²⁹¹ Methyl F CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b²⁹² Methyl F CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b²⁹³ Methyl F CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1b²⁹⁴ Methyl F CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b²⁹⁵ Methyl F CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1b²⁹⁶ Methyl F CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1b²⁹⁷ Methyl F CONH₂ H H 3-(2-Hydroxy H ethoxy)ethyl 1b²⁹⁸ Methyl F CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1b²⁹⁹ Methyl F CONH₂ 3-(4-Hydroxy H H H ethoxy)propyl 1b³⁰⁰ Methyl F CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b³⁰¹ Methyl F CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1b³⁰² Methyl F CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b³⁰³ Methyl F CONH₂ 3-Isopropoxy-propyl H H H 1b³⁰⁴ Methyl F CONH₂ 3-Isopropoxy-propyl H Phenyl H 1b³⁰⁵ Methyl F CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b³⁰⁶ Methyl F CONH₂ 3-Ethoxy-propyl H H H 1b³⁰⁷ Methyl F CONH₂ 3-Ethoxy-propyl H Phenyl H 1b³⁰⁸ Methyl F CONH₂ 3-Ethoxybutyl H 3-Ethoxybutyl H 1b³⁰⁹ Methyl F CONH₂ 3-Ethoxybutyl H H H 1b³¹⁰ Methyl F CONH₂ 3-Ethoxybutyl H Phenyl H 1b³¹¹ Methyl F CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1b³¹² NHCOCH₃ OMe CONH₂ 2-Methoxyethyl H Butyl H 1b³¹³ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1b³¹⁴ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1b³¹⁵ NHCOCH₃ OMe CONH₂ Butyl Butyl 2-Hydroxyethyl H 1b³¹⁶ NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1b³¹⁷ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1b³¹⁸ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1b³¹⁹ NHCOCH₃ OMe CONH₂ 2-Chloro propyl H 2-Ethylhexyl H 1b³²⁰ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b³²¹ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b³²² NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1b³²³ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1b³²⁴ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1b³²⁵ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1b³²⁶ NHCOCH₃ OMe CONH₂ H H 3-(4-Hydroxy H ethoxy)propyl 1b³²⁷ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1b³²⁸ NHCOCH₃ OMe CONH₂ 3-(4-Hydroxy H H H ethoxy)propyl 1b³²⁹ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b³³⁰ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1b³³¹ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b³³² NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1b³³³ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1b³³⁴ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b³³⁵ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1b³³⁶ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1b³³⁷ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1b³³⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H H H 1b³³⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H Phenyl H 1b³⁴⁰ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1b³⁴¹ NHCOCH₃ OMe CONH₂ Butyl Bu 2-Hydroxy ethyl H 1b³⁴² NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1b³⁴³ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1b³⁴⁴ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1b³⁴⁵ NHCOCH₃ OMe CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1b³⁴⁶ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1b³⁴⁷ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1b³⁴⁸ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1b³⁴⁹ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxyethyl H Butyl H 1b³⁵⁰ NHCOCH₃ OMe CONH₂ 2-(Ethyl sulfonyl) ethanol H Butyl H 1b³⁵¹ NHCOCH₃ OMe CONH₂ H H 3-(2-Hydroxy ethoxy) H propyl 1b³⁵² NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1b³⁵³ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1b³⁵⁴ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1b³⁵⁵ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1b³⁵⁶ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1b³⁵⁷ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1b³⁵⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1b³⁵⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1b³⁶⁰ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1b³⁶¹ NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H 3-Ethoxybutyl H 1b³⁶² NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H H H 1b³⁶³ NHCOCH₃ OMe CONH₂ 3-Ethoxybutyl H Phenyl H 1b³⁶⁴ NHCOCH₃ OMe CONH₂ 4-(2-hydroxy- H H H ethanesulfonyl)-phenyl

Further particularly preferred embodiments of the present invention are dyes of formula (1c) and mixtures thereof:

wherein R^(1c), R^(2c), R^(3c) and R^(4c) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5c), R^(6c), R^(7c) and R^(8c) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9c) and R^(15c) independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10c) and R^(16c) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstiuted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl, R^(11c), R^(12c) R^(13c), R^(14c), R^(17c), R^(18c), R^(19c) and R^(20c) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In the most preferred dyes of formula (1c):

R^(2c) and R^(4c) is SO₃M,

R^(1c) and R^(2c) is hydrogen,

R^(5c), R^(6c), R^(7c) and R^(8c) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino,

R^(9c) and R^(15c) independent of each other is cyano or carbamoyl,

R^(10c) and F^(16c) is methyl, R^(11c), R^(12c) R^(13c), R^(14c), R^(17c), R^(18c), R^(19c) and R^(20c) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of such preferred dyes of formula (1c) are the compounds of the formulae (1c¹ to 1c³⁶⁴) and mixtures thereof:

Structure R^(5c)/R^(7c) R^(6c)/R^(8c) R^(9c)/R^(16c) R^(11c)/R^(17c) R^(12c)/R^(18c) R^(13c)/R^(19c) R^(14c)/R^(20c) 1c¹ Methyl Methyl CN Methyl H Methyl H 1c² Methyl Methyl CN Ethyl H Ethyl H 1c³ Methyl Methyl CN Propyl H Propyl H 1c⁴ Methyl Methyl CN Butyl H Butyl H 1c⁵ Methyl Methyl CN Pentyl H Pentyl H 1c⁶ Methyl Methyl CN Hexyl H Hexyl H 1c⁷ Methyl Methyl CN Cyclobutyl H Cyclobutyl H 1c⁸ Methyl Methyl CN Cyclopentyl H Cyclopentyl H 1c⁹ Methyl Methyl CN Cyclohexyl H Cyclohexyl H 1c¹⁰ Methyl Methyl CN 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1c¹¹ Methyl Methyl CN 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1c¹² Methyl Methyl CN Isopropyl H Isopropyl H 1c¹³ Methyl Methyl CN Sec-butyl H Sec-butyl H 1c¹⁴ Methyl Methyl CN 2-Methylbutyl H 2-Methylbutyl H 1c¹⁵ Methyl Methyl CN 1-Ethylpropyl H 1-Ethylpropyl H 1c¹⁶ Methyl Methyl CN 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1c¹⁷ Methyl Methyl CN Tert-butyl H Tert-butyl H 1c¹⁸ Methyl Methyl CN 3-Methylbutyl H 3-Methylbutyl H 1c¹⁹ Methyl Methyl CN Pentan-2-yl H Pentan-2-yl H 1c²⁰ Methyl Methyl CN 2-Ethylhexyl H 2-Ethylhexyl H 1c²¹ Methyl Methyl CN 2,2-Dimethylpropyl H 2,2-Dimethylpropyl H 1c²² Methyl Methyl CN Phenyl H Phenyl H 1c²³ Methyl Methyl CN Benzyl H Benzyl H 1c²⁴ Methyl Methyl CONH₂ Methyl H Methyl H 1c²⁵ Methyl Methyl CONH₂ Ethyl H Ethyl H 1c²⁶ Methyl Methyl CONH₂ Propyl H Propyl H 1c²⁷ Methyl Methyl CONH₂ Butyl H Butyl H 1c²⁸ Methyl Methyl CONH₂ Pentyl H Pentyl H 1c²⁹ Methyl Methyl CONH₂ Hexyl H Hexyl H 1c³⁰ Methyl Methyl CONH₂ Cyclobutyl H Cyclobutyl H 1c³¹ Methyl Methyl CONH₂ Cyclopentyl H Cyclopentyl H 1c³² Methyl Methyl CONH₂ Cyclohexyl H Cyclohexyl H 1c³³ Methyl Methyl CONH₂ 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1c³⁴ Methyl Methyl CONH₂ 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1c³⁵ Methyl Methyl CONH₂ Isopropyl H Isopropyl H 1c³⁶ Methyl Methyl CONH₂ Sec-butyl H Sec-butyl H 1c³⁷ Methyl Methyl CONH₂ 2-Methylbutyl H 2-Methylbutyl H 1c³⁸ Methyl Methyl CONH₂ 1-Ethylpropyl H 1-Ethylpropyl H 1c³⁹ Methyl Methyl CONH₂ 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1c⁴⁰ Methyl Methyl CONH₂ Tert-butyl H Tert-butyl H 1c⁴¹ Methyl Methyl CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1c⁴² Methyl Methyl CONH₂ Pentan-2-yl H Pentan-2-yl H 1c⁴³ Methyl Methyl CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1c⁴⁴ Methyl Methyl CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1c⁴⁵ Methyl Methyl CONH₂ Phenyl H Phenyl H 1c⁴⁶ Methyl Methyl CONH₂ Benzyl H Benzyl H 1c⁴⁷ Methyl F CN Methyl H Methyl H 1c⁴⁸ Methyl F CN Ethyl H Ethyl H 1c⁴⁹ Methyl F CN Propyl H Propyl H 1c⁵⁰ Methyl F CN Butyl H Butyl H 1c⁵¹ Methyl F CN Pentyl H Pentyl H 1c⁵² Methyl F CN Hexyl H Hexyl H 1c⁵³ Methyl F CN Cyclobutyl H Cyclobutyl H 1c⁵⁴ Methyl F CN Cyclopentyl H Cyclopentyl H 1c⁵⁵ Methyl F CN Cyclohexyl H Cyclohexyl H 1c⁵⁶ Methyl F CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1c⁵⁷ Methyl F CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1c⁵⁸ Methyl F CN Isopropyl H Isopropyl H 1c⁵⁹ Methyl F CN Sec-butyl H Sec-butyl H 1c⁶⁰ Methyl F CN 2-Methyl butyl H 2-Methyl H butyl 1c⁶¹ Methyl F CN 1-Ethyl propyl H 1-Ethyl propyl H 1c⁶² Methyl F CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1c⁶³ Methyl F CN Tert-butyl H Tert-butyl H 1c⁶⁴ Methyl F CN 3-Methyl butyl H 3-Methyl butyl H 1c⁶⁵ Methyl F CN Pentan-2-yl H Pentan-2-yl H 1c⁶⁶ Methyl F CN 2-Ethylhexyl H 2-Ethylhexyl H 1c⁶⁷ Methyl F CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1c⁶⁸ Methyl F CN Phenyl H Phenyl H 1c⁶⁹ Methyl F CN Benzyl H Benzyl H 1c⁷⁰ Methyl F CONH₂ Methyl H Methyl H 1c⁷¹ Methyl F CONH₂ Ethyl H Ethyl H 1c⁷² Methyl F CONH₂ Propyl H Propyl H 1c⁷³ Methyl F CONH₂ Butyl H Butyl H 1c⁷⁴ Methyl F CONH₂ Pentyl H Pentyl H 1c⁷⁵ Methyl F CONH₂ Hexyl H Hexyl H 1c⁷⁶ Methyl F CONH₂ Cyclobutyl H Cyclobutyl H 1c⁷⁷ Methyl F CONH₂ Cyclopentyl H Cyclopentyl H 1c⁷⁸ Methyl F CONH₂ Cyclohexyl H Cyclohexyl H 1c⁷⁹ Methyl F CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1c⁸⁰ Methyl F CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1c⁸¹ Methyl F CONH₂ Isopropyl H Isopropyl H 1c⁸² Methyl F CONH₂ Sec-butyl H Sec-butyl H 1c⁸³ Methyl F CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1c⁸⁴ Methyl F CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1c⁸⁵ Methyl F CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1c⁸⁶ Methyl F CONH₂ Tert-butyl H Tert-butyl H 1c⁸⁷ Methyl F CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1c⁸⁸ Methyl F CONH₂ Pentan-2-yl H Pentan-2-yl H 1c⁸⁹ Methyl F CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1c⁹⁰ Methyl F CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1c⁹¹ Methyl F CONH₂ Phenyl H Phenyl H 1c⁹² Methyl F CONH₂ Benzyl H Benzyl H 1c⁹³ NHCOCH₃ OMe CN Methyl H Methyl H 1c⁹⁴ NHCOCH₃ OMe CN Ethyl H Ethyl H 1c⁹⁵ NHCOCH₃ OMe CN Propyl H Propyl H 1c⁹⁶ NHCOCH₃ OMe CN Butyl H Butyl H 1c⁹⁷ NHCOCH₃ OMe CN Pentyl H Pentyl H 1c⁹⁸ NHCOCH₃ OMe CN Hexyl H Hexyl H 1c⁹⁹ NHCOCH₃ OMe CN Cyclobutyl H Cyclobutyl H 1c¹⁰⁰ NHCOCH₃ OMe CN Cyclopentyl H Cyclopentyl H 1c¹⁰¹ NHCOCH₃ OMe CN Cyclohexyl H Cyclohexyl H 1c¹⁰² NHCOCH₃ OMe CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1c¹⁰³ NHCOCH₃ OMe CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1c¹⁰⁴ NHCOCH₃ OMe CN Isopropyl H Isopropyl H 1c¹⁰⁵ NHCOCH₃ OMe CN Sec-butyl H Sec-butyl H 1c¹⁰⁶ NHCOCH₃ OMe CN 2-Methyl butyl H 2-Methyl H butyl 1c¹⁰⁷ NHCOCH₃ OMe CN 1-Ethyl propyl H 1-Ethyl propyl H 1c¹⁰⁸ NHCOCH₃ OMe CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1c¹⁰⁹ NHCOCH₃ OMe CN Tert-butyl H Tert-butyl H 1c¹¹⁰ NHCOCH₃ OMe CN 3-Methyl butyl H 3-Methyl butyl H 1c¹¹¹ NHCOCH₃ OMe CN Pentan-2-yl H Pentan-2-yl H 1c¹¹² NHCOCH₃ OMe CN 2-Ethylhexyl H 2-Ethylhexyl H 1c¹¹³ NHCOCH₃ OMe CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1c¹¹⁴ NHCOCH₃ OMe CN Phenyl H Phenyl H 1c¹¹⁵ NHCOCH₃ OMe CN Benzyl H Benzyl H 1c¹¹⁶ NHCOCH₃ OMe CONH₂ Methyl H Methyl H 1c¹¹⁷ NHCOCH₃ OMe CONH₂ Ethyl H Ethyl H 1c¹¹⁸ NHCOCH₃ OMe CONH₂ Propyl H Propyl H 1c¹¹⁹ NHCOCH₃ OMe CONH₂ Butyl H Butyl H 1c¹²⁰ NHCOCH₃ OMe CONH₂ Pentyl H Pentyl H 1c¹²¹ NHCOCH₃ OMe CONH₂ Hexyl H Hexyl H 1c¹²² NHCOCH₃ OMe CONH₂ Cyclobutyl H Cyclobutyl H 1c¹²³ NHCOCH₃ OMe CONH₂ Cyclopentyl H Cyclopentyl H 1c¹²⁴ NHCOCH₃ OMe CONH₂ Cyclohexyl H Cyclohexyl H 1c¹²⁵ NHCOCH₃ OMe CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1c¹²⁶ NHCOCH₃ OMe CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1c¹²⁷ NHCOCH₃ OMe CONH₂ Isopropyl H Isopropyl H 1c¹²⁸ NHCOCH₃ OMe CONH₂ Sec-butyl H Sec-butyl H 1c¹²⁹ NHCOCH₃ OMe CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1c¹³⁰ NHCOCH₃ OMe CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1c¹³¹ NHCOCH₃ OMe CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1c¹³² NHCOCH₃ OMe CONH₂ Tert-butyl H Tert-butyl H 1c¹³³ NHCOCH₃ OMe CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1c¹³⁴ NHCOCH₃ OMe CONH₂ Pentan-2-yl H Pentan-2-yl H 1c¹³⁵ NHCOCH₃ OMe CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1c¹³⁶ NHCOCH₃ OMe CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1c¹³⁷ NHCOCH₃ OMe CONH₂ Phenyl H Phenyl H 1c¹³⁸ NHCOCH₃ OMe CONH₂ Benzyl H Benzyl H 1c¹³⁹ Methyl Methyl CN 2-Methoxyethyl H Butyl H 1c¹⁴⁰ Methyl Methyl CN 3-Methoxy propyl H 3-Methoxy propyl H 1c¹⁴¹ Methyl Methyl CN 3-Methoxy propyl H Butyl H 1c¹⁴² Methyl Methyl CN Butyl Butyl 2-Hydroyethyl H 1c¹⁴³ Methyl Methyl CN Isopropyl Isopropyl 2-Hydroyethyl H 1c¹⁴⁴ Methyl Methyl CN 2-Fluoro ethyl H Butyl H 1c¹⁴⁵ Methyl Methyl CN 2-Chloro ethyl H 2-Ethylhexyl H 1c¹⁴⁶ Methyl Methyl CN 3-Chloro propyl H 2-Ethylhexyl H 1c¹⁴⁷ Methyl Methyl CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c¹⁴⁸ Methyl Methyl CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c¹⁴⁹ Methyl Methyl CN 2-(2-Hydroxy ethoxy) H Butyl H propyl 1c¹⁵⁰ Methyl Methyl CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c¹⁵¹ Methyl Methyl CN H H 2-(2-Hydroxy ethoxy) H propyl 1c¹⁵² Methyl Methyl CN H H 2-(2-Hydroxy H ethoxy)ethyl 1c¹⁵³ Methyl Methyl CN H H 3-(4-Hydroxy H ethoxy)propyl 1c¹⁵⁴ Methyl Methyl CN 2-(2-Hydroxy H H H ethoxy)ethyl 1c¹⁵⁵ Methyl Methyl CN 3-(4-Hydroxy H H H ethoxy)propyl 1c¹⁵⁶ Methyl Methyl CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1c¹⁵⁷ Methyl Methyl CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1c¹⁵⁸ Methyl Methyl CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c¹⁵⁹ Methyl Methyl CN 3-Isopropoxy-propyl H H H 1c¹⁶⁰ Methyl Methyl CN 3-Isopropoxy-propyl H Phenyl H 1c¹⁶¹ Methyl Methyl CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c¹⁶² Methyl Methyl CN 3-Ethoxy-propyl H H H 1c¹⁶³ Methyl Methyl CN 3-Ethoxy-propyl H Phenyl H 1c¹⁶⁴ Methyl Methyl CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1c¹⁶⁵ Methyl Methyl CN 3-Ethoxybutyl H H H 1c¹⁶⁶ Methyl Methyl CN 3-Ethoxybutyl H Phenyl H 1c¹⁶⁷ Methyl Methyl CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1c¹⁶⁸ Methyl F CN 2-Methoxyethyl H Butyl H 1c¹⁶⁹ Methyl F CN 3-Methoxy propyl H 3-Methoxy propyl H 1c¹⁷⁰ Methyl F CN 3-Methoxy propyl H Butyl H 1c¹⁷¹ Methyl F CN Butyl Butyl 2-Hydoxy ethyl H 1c¹⁷² Methyl F CN Isopropyl Isopropyl 2-Hydoxy ethyl H 1c¹⁷³ Methyl F CN 2-Fluoro ethyl H Butyl H 1c¹⁷⁴ Methyl F CN 2-Chloro ethyl H 2-Ethyl hexyl H 1c¹⁷⁵ Methyl F CN 3-Chloro propyl H 2-Ethyl hexyl H 1c¹⁷⁶ Methyl F CN 2-(2- H Butyl H Hydroxethylsulfanyl)- ethyl 1c¹⁷⁷ Methyl F CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c¹⁷⁸ Methyl F CN 2-Hydroxy ethoxy H Butyl H propyl 1c¹⁷⁹ Methyl F CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c¹⁸⁰ Methyl F CN H H 2-(2-Hydroxy ethoxy) H propyl 1c¹⁸¹ Methyl F CN H H 2-(2-Hydroxy H ethoxy)ethyl 1c¹⁸² Methyl F CN H H 3-(2-Hydroxy H ethoxy)propyl 1c¹⁸³ Methyl F CN 2-(2-Hydoxy H H H ethoxy)ethyl 1c¹⁸⁴ Methyl F CN 3-(2-Hydroxy H H H ethoxy)propyl 1c¹⁸⁵ Methyl F CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1c¹⁸⁶ Methyl F CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1c¹⁸⁷ Methyl F CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c¹⁸⁸ Methyl F CN 3-Isopropoxy-propyl H H H 1c¹⁸⁹ Methyl F CN 3-Isopropoxy-propyl H Phenyl H 1c¹⁹⁰ Methyl F CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c¹⁹¹ Methyl F CN 3-Ethoxy-propyl H H 1c¹⁹² Methyl F CN 3-Ethoxy-propyl H Phenyl H 1c¹⁹³ Methyl F CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1c¹⁹⁴ Methyl F CN 3-Ethoxybutyl H H 1c¹⁹⁵ Methyl F CN 3-Ethoxybutyl H Phenyl H 1c¹⁹⁶ Methyl F CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1c¹⁹⁷ NHCOCH₃ OMe CN 2-Methoxyethyl H Butyl H 1c¹⁹⁸ NHCOCH₃ OMe CN 3-Methoxy propyl H 3-Methoxy propyl H 1c¹⁹⁹ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1c²⁰⁰ NHCOCH₃ OMe CN Butyl Butyl 2-Hydroxyethyl H 1c²⁰¹ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxyethyl H 1c²⁰² NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1c²⁰³ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethylhexyl H 1c²⁰⁴ NHCOCH₃ OMe CN 3-Chloro propyl H 2-Ethylhexyl H 1c²⁰⁵ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c²⁰⁶ NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c²⁰⁷ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1c²⁰⁸ NHCOCH₃ OMe CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c²⁰⁹ NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy) H propyl 1c²¹⁰ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1c²¹¹ NHCOCH₃ OMe CN H H 3-(2-Hydroxy H ethoxy)propyl 1c²¹² NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1c²¹³ NHCOCH₃ OMe CN 3-(2-Hydroxy H H H ethoxy)propyl 1c²¹⁴ NHCOCH₃ OMe CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1c²¹⁵ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1c²¹⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c²¹⁷ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1c²¹⁸ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1c²¹⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c²²⁰ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1c²²¹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1c²²² NHCOCH₃ OMe CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1c²²³ NHCOCH₃ OMe CN 3-Ethoxybutyl H H H 1c²²⁴ NHCOCH₃ OMe CN 3-Ethoxybutyl H Phenyl H 1c²²⁵ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1c²²⁶ NHCOCH₃ OMe CN Butyl Bu 2-Hydroxyethyl H 1c²²⁷ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxyethyl H 1c²²⁸ NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1c²²⁹ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethylhexyl H 1c²³⁰ NHCOCH₃ OMe CN 2-Chloro propyl H 2-Ethylhexyl H 1c²³¹ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c²³² NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c²³³ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1c²³⁴ NHCOCH₃ OMe CN 2-Hydroxy ethoxyethyl H Butyl H 1c²³⁵ NHCOCH₃ OMe CN 2-(Ethyl sulfonyl) ethanol H Butyl H 1c²³⁶ NHCOCH₃ OMe CN H H (2-Hydroxy ethoxy) H propyl 1c²³⁷ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1c²³⁸ NHCOCH₃ OMe CN H H 3-(2-Hydroxy H ethoxy)propyl 1c²³⁹ NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1c²⁴⁰ NHCOCH₃ OMe CN 3-(2-Hydroxy H H H ethoxy)propyl 1c²⁴¹ NHCOCH₃ OMe CN H H (2-Hydroxy H ethoxy)ethyl 1c²⁴² NHCOCH₃ OMe CN Phenyl H (2-Hydroxy H ethoxy)ethyl 1c²⁴³ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1c²⁴⁴ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c²⁴⁵ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1c²⁴⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1c²⁴⁷ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c²⁴⁸ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1c²⁴⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1c²⁵⁰ NHCOCH₃ OMe CN 3-Ethoxybutyl H 3-Ethoxybutyl H 1c²⁵¹ NHCOCH₃ OMe CN 3-Ethoxybutyl H H H 1c²⁵² NHCOCH₃ OMe CN 3-Ethoxybutyl H Phenyl H 1c²⁵³ NHCOCH₃ OMe CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1c²⁵⁴ Methyl Methyl CONH₂ 2-Methoxyethyl H Butyl H 1c²⁵⁵ Methyl Methyl CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1c²⁵⁶ Methyl Methyl CONH₂ 3-Methoxy propyl H Butyl H 1c²⁵⁷ Methyl Methyl CONH₂ Butyl Butyl 2-Hydroxyethyl H 1c²⁵⁸ Methyl Methyl CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1c²⁵⁹ Methyl Methyl CONH₂ 2-Fluoro ethyl H Butyl H 1c²⁶⁰ Methyl Methyl CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1c²⁶¹ Methyl Methyl CONH₂ 3-Chloro propyl H 2-Ethylhexyl H 1c²⁶² Methyl Methyl CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c²⁶³ Methyl Methyl CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c²⁶⁴ Methyl Methyl CONH₂ 2-Hydroxy ethoxy propyl H Butyl H 1c²⁶⁵ Methyl Methyl CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c²⁶⁶ Methyl Methyl CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1c²⁶⁷ Methyl Methyl CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1c²⁶⁸ Methyl Methyl CONH₂ H H 3-(2-Hydroxy H ethoxy)propyl 1c²⁶⁹ Methyl Methyl CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1c²⁷⁰ Methyl Methyl CONH₂ 3-(2-Hydroxy H H H ethoxy)propyl 1c²⁷¹ Methyl Methyl CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1c²⁷² Methyl Methyl CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1c²⁷³ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c²⁷⁴ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H H H 1c²⁷⁵ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H Phenyl H 1c²⁷⁶ Methyl Methyl CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c²⁷⁷ Methyl Methyl CONH₂ 3-Ethoxy-propyl H H H 1c²⁷⁸ Methyl Methyl CONH₂ 3-Ethoxy-propyl H Phenyl H 1c²⁷⁹ Methyl Methyl CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1c²⁸⁰ Methyl Methyl CONH₂ 3-Ethoxy butyl H H H 1c²⁸¹ Methyl Methyl CONH₂ 3-Ethoxy butyl H Phenyl H 1c²⁸² Methyl Methyl CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1c²⁸³ Methyl F CONH₂ 2-Methoxyethyl H Butyl H 1c²⁸⁴ Methyl F CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1c²⁸⁵ Methyl F CONH₂ 3-Methoxy propyl H Butyl H 1c²⁸⁶ Methyl F CONH₂ Butyl Butyl 2-Hydroxyethyl H 1c²⁸⁷ Methyl F CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1c²⁸⁸ Methyl F CONH₂ 2-Fluoro ethyl H Butyl H 1c²⁸⁹ Methyl F CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1c²⁹⁰ Methyl F CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1c²⁹¹ Methyl F CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c²⁹² Methyl F CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c²⁹³ Methyl F CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1c²⁹⁴ Methyl F CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c²⁹⁵ Methyl F CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1c²⁹⁶ Methyl F CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1c²⁹⁷ Methyl F CONH₂ H H 3-(2-Hydroxy H ethoxy)ethyl 1c²⁹⁸ Methyl F CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1c²⁹⁹ Methyl F CONH₂ 3-(2-Hydroxy H H H ethoxy)ethyl 1c³⁰⁰ Methyl F CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1c³⁰¹ Methyl F CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1c³⁰² Methyl F CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c³⁰³ Methyl F CONH₂ 3-Isopropoxy-propyl H H H 1c³⁰⁴ Methyl F CONH₂ 3-Isopropoxy-propyl H Phenyl H 1c³⁰⁵ Methyl F CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c³⁰⁶ Methyl F CONH₂ 3-Ethoxy-propyl H H H 1c³⁰⁷ Methyl F CONH₂ 3-Ethoxy-propyl H Phenyl H 1c³⁰⁸ Methyl F CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1c³⁰⁹ Methyl F CONH₂ 3-Ethoxy butyl H H H 1c³¹⁰ Methyl F CONH₂ 3-Ethoxy butyl H Phenyl H 1c³¹¹ Methyl F CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1c³¹² NHCOCH₃ OMe CONH₂ 2-Methoxyethyl H Butyl H 1c³¹³ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1c³¹⁴ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1c³¹⁵ NHCOCH₃ OMe CONH₂ Butyl Butyl 2-Hydroxyethyl H 1c³¹⁶ NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxyethyl H 1c³¹⁷ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1c³¹⁸ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1c³¹⁹ NHCOCH₃ OMe CONH₂ 2-Chloro propyl H 2-Ethylhexyl H 1c³²⁰ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c³²¹ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c³²² NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1c³²³ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1c³²⁴ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1c³²⁵ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy- H ethoxy)ethyl 1c³²⁶ NHCOCH₃ OMe CONH₂ H H 3-(2-Hydroxy- H ethoxy)propyl 1c³²⁷ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxy- H H H ethoxy)ethyl 1c³²⁸ NHCOCH₃ OMe CONH₂ 3-(2-Hydroxy- H H H ethoxy)propyl 1c³²⁹ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy- H ethoxy)ethyl 1c³³⁰ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1c³³¹ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c³³² NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1c³³³ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1c³³⁴ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c³³⁵ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1c³³⁶ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1c³³⁷ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H 3-Ethoxybutyl H 1c³³⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H H H 1c³³⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H Phenyl H 1c³⁴⁰ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1c³⁴¹ NHCOCH₃ OMe CONH₂ Butyl Butyl 2-Hydroxy ethyl H 1c³⁴² NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1c³⁴³ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1c³⁴⁴ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethylhexyl H 1c³⁴⁵ NHCOCH₃ OMe CONH₂ 3-Chloro propyl H 2-Ethylhexyl H 1c³⁴⁶ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1c³⁴⁷ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1c³⁴⁸ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1c³⁴⁹ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxyethyl H Butyl H 1c³⁵⁰ NHCOCH₃ OMe CONH₂ 2-(Ethyl sulfonyl) ethanol H Butyl H 1c³⁵¹ NHCOCH₃ OMe CONH₂ H H 3-(2-Hydroxy ethoxy) H propyl 1c³⁵² NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy- H ethoxy)ethyl 1c³⁵³ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy- H ethoxy)ethyl 1c³⁵⁴ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1c³⁵⁵ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1c³⁵⁶ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1c³⁵⁷ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1c³⁵⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1c³⁵⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1c³⁶⁰ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1c³⁶¹ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1c³⁶² NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H H H 1c³⁶³ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H Phenyl H 1c³⁶⁴ NHCOCH₃ OMe CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl Further particularly preferred embodiments of the present invention are dyes of formula (1d) and mixtures thereof

wherein R^(1d), R^(2d), R^(3d) and R^(4d) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M whereby at least two of them are SO₃M, R^(5d), R^(6d), R^(7d) and R^(8d) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino R^(9d) and R^(15d) independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10d) and R^(16d) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, (C₅-C₇)-cycloalkyi or substituted (C₅-C₇)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, Cert-butyl and methylbutyl, R^(11d), R^(12d) R^(13d), R^(14d), R^(17d), R^(18d), R^(19d) and R^(20d) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In the most preferred dyes of formula (1d):

R^(1d) and R^(3d) is SO₃M, R^(2d) and R^(4d) is hydrogen, R^(5d), R^(6d), R^(7d) and R^(8d) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9d) and R^(15d) independent of each other is cyano or carbamoyl, R^(10d) and R^(16d) is methyl, R^(11d), R^(12d) R^(13d), R^(14d), R^(17d), R^(16d), R^(19d) and R^(20d) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of the formula (1d) are the compounds of formulae (1d¹ to 1 d³⁶⁴) and mixtures thereof:

R^(14d)/ Structure R^(5d)/R^(7d) R^(6d)/R^(8d) R^(9d)/R^(16d) R^(11d)/R^(17d) R^(12d)/R^(18d) R^(13d)/R^(19d) R^(20d) 1d¹ Methyl Methyl CN Methyl H Methyl H 1d² Methyl Methyl CN Ethyl H Ethyl H 1d³ Methyl Methyl CN Propyl H Propyl H 1d⁴ Methyl Methyl CN Butyl H Butyl H 1d⁵ Methyl Methyl CN Pentyl H Pentyl H 1d⁶ Methyl Methyl CN Hexyl H Hexyl H 1d⁷ Methyl Methyl CN Cyclobutyl H Cyclobutyl H 1d⁸ Methyl Methyl CN Cyclopentyl H Cyclopentyl H 1d⁹ Methyl Methyl CN Cyclohexyl H Cyclohexyl H 1d¹⁰ Methyl Methyl CN 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1d¹¹ Methyl Methyl CN 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1d¹² Methyl Methyl CN Isopropyl H Isopropyl H 1d¹³ Methyl Methyl CN Sec-butyl H Sec-butyl H 1d¹⁴ Methyl Methyl CN 2-Methylbutyl H 2-Methylbutyl H 1d¹⁵ Methyl Methyl CN 1-Ethylpropyl H 1-Ethylpropyl H 1d¹⁶ Methyl Methyl CN 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1d¹⁷ Methyl Methyl CN Tert-butyl H Tert-butyl H 1d¹⁸ Methyl Methyl CN 3-Methylbutyl H 3-Methylbutyl H 1d¹⁹ Methyl Methyl CN Pentan-2-yl H Pentan-2-yl H 1d²⁰ Methyl Methyl CN 2-Ethylhexyl H 2-Ethylhexyl H 1d²¹ Methyl Methyl CN 2,2-Dimethylpropyl H 2,2-Dimethylpropyl H 1d²² Methyl Methyl CN Phenyl H Phenyl H 1d²³ Methyl Methyl CN Benzyl H Benzyl H 1d²⁴ Methyl Methyl CONH₂ Methyl H Methyl H 1d²⁵ Methyl Methyl CONH₂ Ethyl H Ethyl H 1d²⁶ Methyl Methyl CONH₂ Propyl H Propyl H 1d²⁷ Methyl Methyl CONH₂ Butyl H Butyl H 1d²⁸ Methyl Methyl CONH₂ Pentyl H Pentyl H 1d²⁹ Methyl Methyl CONH₂ Hexyl H Hexyl H 1d³⁰ Methyl Methyl CONH₂ Cyclobutyl H Cyclobutyl H 1d³¹ Methyl Methyl CONH₂ Cyclopentyl H Cyclopentyl H 1d³² Methyl Methyl CONH₂ Cyclohexyl H Cyclohexyl H 1d³³ Methyl Methyl CONH₂ 2-Methylcyclohexyl H 2-Methylcyclohexyl H 1d³⁴ Methyl Methyl CONH₂ 3-Methylcyclohexyl H 3-Methylcyclohexyl H 1d³⁵ Methyl Methyl CONH₂ Isopropyl H Isopropyl H 1d³⁶ Methyl Methyl CONH₂ Sec-butyl H Sec-butyl H 1d³⁷ Methyl Methyl CONH₂ 2-Methylbutyl H 2-Methylbutyl H 1d³⁸ Methyl Methyl CONH₂ 1-Ethylpropyl H 1-Ethylpropyl H 1d³⁹ Methyl Methyl CONH₂ 1,2-Dimethylpropyl H 1,2-Dimethylpropyl H 1d⁴⁰ Methyl Methyl CONH₂ Tert-butyl H Tert-butyl H 1d⁴¹ Methyl Methyl CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1d⁴² Methyl Methyl CONH₂ Pentan-2-yl H Pentan-2-yl H 1d⁴³ Methyl Methyl CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1d⁴⁴ Methyl Methyl CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1d⁴⁵ Methyl Methyl CONH₂ Phenyl H Phenyl H 1d⁴⁶ Methyl Methyl CONH₂ Benzyl H Benzyl H 1d⁴⁷ Methyl F CN Methyl H Methyl H 1d⁴⁸ Methyl F CN Ethyl H Ethyl H 1d⁴⁹ Methyl F CN Propyl H Propyl H 1d⁵⁰ Methyl F CN Butyl H Butyl H 1d⁵¹ Methyl F CN Pentyl H Pentyl H 1d⁵² Methyl F CN Hexyl H Hexyl H 1d⁵³ Methyl F CN Cyclobutyl H Cyclobutyl H 1d⁵⁴ Methyl F CN Cyclopentyl H Cyclopentyl H 1d⁵⁵ Methyl F CN Cyclohexyl H Cyclohexyl H 1d⁵⁶ Methyl F CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1d⁵⁷ Methyl F CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1d⁵⁸ Methyl F CN Isopropyl H Isopropyl H 1d⁵⁹ Methyl F CN Sec-butyl H Sec-butyl H 1d⁶⁰ Methyl F CN 2-Methyl butyl H 2-Methyl H butyl 1d⁶¹ Methyl F CN 1-Ethyl propyl H 1-Ethyl propyl H 1d⁶² Methyl F CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1d⁶³ Methyl F CN Tert-butyl H Tert-butyl H 1d⁶⁴ Methyl F CN 3-Methyl butyl H 3-Methyl butyl H 1d⁶⁵ Methyl F CN Pentan-2-yl H Pentan-2-yl H 1d⁶⁶ Methyl F CN 2-Ethylhexyl H 2-Ethylhexyl H 1d⁶⁷ Methyl F CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1d⁶⁸ Methyl F CN Phenyl H Phenyl H 1d⁶⁹ Methyl F CN Benzyl H Benzyl H 1d⁷⁰ Methyl F CONH₂ Methyl H Methyl H 1d⁷¹ Methyl F CONH₂ Ethyl H Ethyl H 1d⁷² Methyl F CONH₂ Propyl H Propyl H 1d⁷³ Methyl F CONH₂ Butyl H Butyl H 1d⁷⁴ Methyl F CONH₂ Pentyl H Pentyl H 1d⁷⁵ Methyl F CONH₂ Hexyl H Hexyl H 1d⁷⁶ Methyl F CONH₂ Cyclobutyl H Cyclobutyl H 1d⁷⁷ Methyl F CONH₂ Cyclopentyl H Cyclopentyl H 1d⁷⁸ Methyl F CONH₂ Cyclohexyl H Cyclohexyl H 1d⁷⁹ Methyl F CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1d⁸⁰ Methyl F CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1d⁸¹ Methyl F CONH₂ Isopropyl H Isopropyl H 1d⁸² Methyl F CONH₂ Sec-butyl H Sec-butyl H 1d⁸³ Methyl F CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1d⁸⁴ Methyl F CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1d⁸⁵ Methyl F CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1d⁸⁶ Methyl F CONH₂ Tert-butyl H Tert-butyl H 1d⁸⁷ Methyl F CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1d⁸⁸ Methyl F CONH₂ Pentan-2-yl H Pentan-2-yl H 1d⁸⁹ Methyl F CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1d⁹⁰ Methyl F CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1d⁹¹ Methyl F CONH₂ Phenyl H Phenyl H 1d⁹² Methyl F CONH₂ Benzyl H Benzyl H 1d⁹³ NHCOCH₃ OMe CN Methyl H Methyl H 1d⁹⁴ NHCOCH₃ OMe CN Ethyl H Ethyl H 1d⁹⁵ NHCOCH₃ OMe CN Propyl H Propyl H 1d⁹⁶ NHCOCH₃ OMe CN Butyl H Butyl H 1d⁹⁷ NHCOCH₃ OMe CN Pentyl H Pentyl H 1d⁹⁸ NHCOCH₃ OMe CN Hexyl H Hexyl H 1d⁹⁹ NHCOCH₃ OMe CN Cyclobutyl H Cyclobutyl H 1d¹⁰⁰ NHCOCH₃ OMe CN Cyclopentyl H Cyclopentyl H 1d¹⁰¹ NHCOCH₃ OMe CN Cyclohexyl H Cyclohexyl H 1d¹⁰² NHCOCH₃ OMe CN 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1d¹⁰³ NHCOCH₃ OMe CN 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1d¹⁰⁴ NHCOCH₃ OMe CN Isopropyl H Isopropyl H 1d¹⁰⁵ NHCOCH₃ OMe CN Sec-butyl H Sec-butyl H 1d¹⁰⁶ NHCOCH₃ OMe CN 2-Methyl butyl H 2-Methyl H butyl 1d¹⁰⁷ NHCOCH₃ OMe CN 1-Ethyl propyl H 1-Ethyl propyl H 1d¹⁰⁸ NHCOCH₃ OMe CN 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1d¹⁰⁹ NHCOCH₃ OMe CN Tert-butyl H Tert-butyl H 1d¹¹⁰ NHCOCH₃ OMe CN 3-Methyl butyl H 3-Methyl butyl H 1d¹¹¹ NHCOCH₃ OMe CN Pentan-2-yl H Pentan-2-yl H 1d¹¹² NHCOCH₃ OMe CN 2-Ethylhexyl H 2-Ethylhexyl H 1d¹¹³ NHCOCH₃ OMe CN 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1d¹¹⁴ NHCOCH₃ OMe CN Phenyl H Phenyl H 1d¹¹⁵ NHCOCH₃ OMe CN Benzyl H Benzyl H 1d¹¹⁶ NHCOCH₃ OMe CONH₂ Methyl H Methyl H 1d¹¹⁷ NHCOCH₃ OMe CONH₂ Ethyl H Ethyl H 1d¹¹⁸ NHCOCH₃ OMe CONH₂ Propyl H Propyl H 1d¹¹⁹ NHCOCH₃ OMe CONH₂ Butyl H Butyl H 1d¹²⁰ NHCOCH₃ OMe CONH₂ Pentyl H Pentyl H 1d¹²¹ NHCOCH₃ OMe CONH₂ Hexyl H Hexyl H 1d¹²² NHCOCH₃ OMe CONH₂ Cyclobutyl H Cyclobutyl H 1d¹²³ NHCOCH₃ OMe CONH₂ Cyclopentyl H Cyclopentyl H 1d¹²⁴ NHCOCH₃ OMe CONH₂ Cyclohexyl H Cyclohexyl H 1d¹²⁵ NHCOCH₃ OMe CONH₂ 2-Methyl cyclohexyl H 2-Methyl cyclohexyl H 1d¹²⁶ NHCOCH₃ OMe CONH₂ 3-Methyl cyclohexyl H 3-Methyl cyclohexyl H 1d¹²⁷ NHCOCH₃ OMe CONH₂ Isopropyl H Isopropyl H 1d¹²⁸ NHCOCH₃ OMe CONH₂ Sec-butyl H Sec-butyl H 1d¹²⁹ NHCOCH₃ OMe CONH₂ 2-Methyl butyl H 2-Methyl H butyl 1d¹³⁰ NHCOCH₃ OMe CONH₂ 1-Ethyl propyl H 1-Ethyl propyl H 1d¹³¹ NHCOCH₃ OMe CONH₂ 1,2-Dimethyl propyl H 1,2-Dimethyl propyl H 1d¹³² NHCOCH₃ OMe CONH₂ Tert-butyl H Tert-butyl H 1d¹³³ NHCOCH₃ OMe CONH₂ 3-Methyl butyl H 3-Methyl butyl H 1d¹³⁴ NHCOCH₃ OMe CONH₂ Pentan-2-yl H Pentan-2-yl H 1d¹³⁵ NHCOCH₃ OMe CONH₂ 2-Ethylhexyl H 2-Ethylhexyl H 1d¹³⁶ NHCOCH₃ OMe CONH₂ 2,2-Dimethyl propyl H 2,2-Dimethyl propyl H 1d¹³⁷ NHCOCH₃ OMe CONH₂ Phenyl H Phenyl H 1d¹³⁸ NHCOCH₃ OMe CONH₂ Benzyl H Benzyl H 1d¹³⁹ Methyl Methyl CN 2-Methoxyethyl H Butyl H 1d¹⁴⁰ Methyl Methyl CN 3-Methoxy propyl H 3-Methoxy propyl H 1d¹⁴¹ Methyl Methyl CN 3-Methoxy propyl H Butyl H 1d¹⁴² Methyl Methyl CN Butyl Butyl 2-Hydroxyethyl H 1d¹⁴³ Methyl Methyl CN Isopropyl Isopropyl 2-Hydroxyethyl H 1d¹⁴⁴ Methyl Methyl CN 2-Fluoro ethyl H Butyl H 1d¹⁴⁵ Methyl Methyl CN 2-Chloro ethyl H 2-Ethylhexyl H 1d¹⁴⁶ Methyl Methyl CN 3-Chloro propyl H 2-Ethylhexyl H 1d¹⁴⁷ Methyl Methyl CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d¹⁴⁸ Methyl Methyl CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d¹⁴⁹ Methyl Methyl CN 2-(2-Hydroxy ethoxy) H Butyl H propyl 1d¹⁵⁰ Methyl Methyl CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d¹⁵¹ Methyl Methyl CN H H 2-(2-Hydroxy ethoxy) H propyl 1d¹⁵² Methyl Methyl CN H H 2-(2-Hydroxy H ethoxy)ethyl 1d¹⁵³ Methyl Methyl CN H H 3-(2-Hydroxy H ethoxy)ethyl 1d¹⁵⁴ Methyl Methyl CN 2-(2-Hydroxy H H H ethoxy)ethyl 1d¹⁵⁵ Methyl Methyl CN 3-(2-Hydroxy H H H ethoxy)ethyl 1d¹⁵⁶ Methyl Methyl CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d¹⁵⁷ Methyl Methyl CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1d¹⁵⁸ Methyl Methyl CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d¹⁵⁹ Methyl Methyl CN 3-Isopropoxy-propyl H H H 1d¹⁶⁰ Methyl Methyl CN 3-Isopropoxy-propyl H Phenyl H 1d¹⁶¹ Methyl Methyl CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d¹⁶² Methyl Methyl CN 3-Ethoxy-propyl H H H 1d¹⁶³ Methyl Methyl CN 3-Ethoxy-propyl H Phenyl H 1d¹⁶⁴ Methyl Methyl CN 3-Ethoxy butyl H 3-Ethoxybutyl H 1d¹⁶⁵ Methyl Methyl CN 3-Ethoxy butyl H H H 1d¹⁶⁶ Methyl Methyl CN 3-Ethoxy butyl H Phenyl H 1d¹⁶⁷ Methyl Methyl CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1d¹⁶⁸ Methyl F CN 2-Methoxyethyl H Butyl H 1d¹⁶⁹ Methyl F CN 3-Methoxy propyl H 3-Methoxy propyl H 1d¹⁷⁰ Methyl F CN 3-Methoxy propyl H Butyl H 1d¹⁷¹ Methyl F CN Butyl Butyl 2-Hydroxy ethyl H 1d¹⁷² Methyl F CN Isopropyl Isopropyl 2-Hydroxy ethyl H 1d¹⁷³ Methyl F CN 2-Fluoro ethyl H Butyl H 1d¹⁷⁴ Methyl F CN 2-Chloro ethyl H 2-Ethyl hexyl H 1d¹⁷⁵ Methyl F CN 3-Chloro propyl H 2-Ethyl hexyl H 1d¹⁷⁶ Methyl F CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d¹⁷⁷ Methyl F CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d¹⁷⁸ Methyl F CN 2-Hydroxy ethoxy H Butyl H propyl 1d¹⁷⁹ Methyl F CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d¹⁸⁰ Methyl F CN H H 2-(2-Hydroxy ethoxy) H propyl 1d¹⁸¹ Methyl F CN H H 2-(2-Hydroxy H ethoxy)ethyl 1d¹⁸² Methyl F CN H H 3-(2-Hydroxy H ethoxy)propyl 1d¹⁸³ Methyl F CN 2-(2-Hydroxy H H H ethoxy)ethyl 1d¹⁸⁴ Methyl F CN 3-(2-Hydroxy H H H ethoxy)propyl 1d¹⁸⁵ Methyl F CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d¹⁸⁶ Methyl F CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1d¹⁸⁷ Methyl F CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d¹⁸⁸ Methyl F CN 3-Isopropoxy-propyl H H H 1d¹⁸⁹ Methyl F CN 3-Isopropoxy-propyl H Phenyl H 1d¹⁹⁰ Methyl F CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d¹⁹¹ Methyl F CN 3-Ethoxy-propyl H H 1d¹⁹² Methyl F CN 3-Ethoxy-propyl H Phenyl H 1d¹⁹³ Methyl F CN 3-Ethoxy butyl H 3-Ethoxy butyl H 1d¹⁹⁴ Methyl F CN 3-Ethoxy butyl H H 1d¹⁹⁵ Methyl F CN 3-Ethoxy butyl H Phenyl H 1d¹⁹⁶ Methyl F CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1d¹⁹⁷ NHCOCH₃ OMe CN 2-Methoxyethyl H Butyl H 1d¹⁹⁸ NHCOCH₃ OMe CN 3-Methoxy propyl H 3-Methoxy propyl H 1d¹⁹⁹ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1d²⁰⁰ NHCOCH₃ OMe CN Butyl Butyl 2-Hydroxyethyl H 1d²⁰¹ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxyethyl H 1d²⁰² NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1d²⁰³ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethylhexyl H 1d²⁰⁴ NHCOCH₃ OMe CN 3-Chloro propyl H 2-Ethylhexyl H 1d²⁰⁵ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d²⁰⁶ NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d²⁰⁷ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1d²⁰⁸ NHCOCH₃ OMe CN 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d²⁰⁹ NHCOCH₃ OMe CN H H 2-(2-Hydroxy ethoxy) H propyl 1d²¹⁰ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1d²¹¹ NHCOCH₃ OMe CN H H 3-(2-Hydroxy H ethoxy)propyl 1d²¹² NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1d²¹³ NHCOCH₃ OMe CN 3-(2-Hydroxy H H H ethoxy)propyl 1d²¹⁴ NHCOCH₃ OMe CN Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d²¹⁵ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1d²¹⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d²¹⁷ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1d²¹⁸ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1d²¹⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d²²⁰ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1d²²¹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1d²²² NHCOCH₃ OMe CN 3-Ethoxy butyl H 3-Ethoxy butyl H 1d²²³ NHCOCH₃ OMe CN 3-Ethoxy butyl H H H 1d²²⁴ NHCOCH₃ OMe CN 3-Ethoxy butyl H Phenyl H 1d²²⁵ NHCOCH₃ OMe CN 3-Methoxy propyl H Butyl H 1d²²⁶ NHCOCH₃ OMe CN Butyl Butyl 2-Hydroxy ethyl H 1d²²⁷ NHCOCH₃ OMe CN Isopropyl Isopropyl 2-Hydroxy ethyl H 1d²²⁸ NHCOCH₃ OMe CN 2-Fluoro ethyl H Butyl H 1d²²⁹ NHCOCH₃ OMe CN 2-Chloro ethyl H 2-Ethyl hexyl H 1d²³⁰ NHCOCH₃ OMe CN 2-Chloro propyl H 2-Ethyl hexyl H 1d²³¹ NHCOCH₃ OMe CN 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d²³² NHCOCH₃ OMe CN 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d²³³ NHCOCH₃ OMe CN 2-Hydroxy ethoxy H Butyl H propyl 1d²³⁴ NHCOCH₃ OMe CN 2-Hydroxy ethoxyethyl H Butyl H 1d²³⁵ NHCOCH₃ OMe CN 2-(Ethyl sulfonyl) ethanol H Butyl H 1d²³⁶ NHCOCH₃ OMe CN H H (2-Hydroxy ethoxy) H propyl 1d²³⁷ NHCOCH₃ OMe CN H H 2-(2-Hydroxy H ethoxy)ethyl 1d²³⁸ NHCOCH₃ OMe CN H H 3-(2-Hydroxy H ethoxy)propyl 1d²³⁹ NHCOCH₃ OMe CN 2-(2-Hydroxy H H H ethoxy)ethyl 1d²⁴⁰ NHCOCH₃ OMe CN 3-(2-Hydroxy H H H ethoxy)propyl 1d²⁴¹ NHCOCH₃ OMe CN H H (2-Hydroxy H ethoxy)ethyl 1d²⁴² NHCOCH₃ OMe CN Phenyl H (2-Hydroxy H ethoxy)ethyl 1d²⁴³ NHCOCH₃ OMe CN 3-(2-Phenoxy-ethoxy)- H H H propyl 1d²⁴⁴ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d²⁴⁵ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H H H 1d²⁴⁶ NHCOCH₃ OMe CN 3-Isopropoxy-propyl H Phenyl H 1d²⁴⁷ NHCOCH₃ OMe CN 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d²⁴⁸ NHCOCH₃ OMe CN 3-Ethoxy-propyl H H H 1d²⁴⁹ NHCOCH₃ OMe CN 3-Ethoxy-propyl H Phenyl H 1d²⁵⁰ NHCOCH₃ OMe CN 3-Ethoxy butyl H 3-Ethoxy butyl H 1d²⁵¹ NHCOCH₃ OMe CN 3-Ethoxy butyl H H H 1d²⁵² NHCOCH₃ OMe CN 3-Ethoxy butyl H Phenyl H 1d²⁵³ NHCOCH₃ OMe CN 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1d²⁵⁴ Methyl Methyl CONH₂ 2-Methoxyethyl H Butyl H 1d²⁵⁵ Methyl Methyl CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1d²⁵⁶ Methyl Methyl CONH₂ 3-Methoxy propyl H Butyl H 1d²⁵⁷ Methyl Methyl CONH₂ Butyl Butyl 2-Hydroxy ethyl H 1d²⁵⁸ Methyl Methyl CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1d²⁵⁹ Methyl Methyl CONH₂ 2-Fluoro ethyl H Butyl H 1d²⁶⁰ Methyl Methyl CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1d²⁶¹ Methyl Methyl CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1d²⁶² Methyl Methyl CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d²⁶³ Methyl Methyl CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d²⁶⁴ Methyl Methyl CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1d²⁶⁵ Methyl Methyl CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d²⁶⁶ Methyl Methyl CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1d²⁶⁷ Methyl Methyl CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1d²⁶⁸ Methyl Methyl CONH₂ H H 3-(2-Hydroxy H ethoxy)propyl 1d²⁶⁹ Methyl Methyl CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1d²⁷⁰ Methyl Methyl CONH₂ 3-(2-Hydroxy H H H ethoxy)propyl 1d²⁷¹ Methyl Methyl CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d²⁷² Methyl Methyl CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1d²⁷³ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d²⁷⁴ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H H H 1d²⁷⁵ Methyl Methyl CONH₂ 3-Isopropoxy-propyl H Phenyl H 1d²⁷⁶ Methyl Methyl CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d²⁷⁷ Methyl Methyl CONH₂ 3-Ethoxy-propyl H H H 1d²⁷⁸ Methyl Methyl CONH₂ 3-Ethoxy-propyl H Phenyl H 1d²⁷⁹ Methyl Methyl CONH₂ 3-Ethoxybutyl H 3-Ethoxybutyl H 1d²⁸⁰ Methyl Methyl CONH₂ 3-Ethoxybutyl H H H 1d²⁸¹ Methyl Methyl CONH₂ 3-Ethoxybutyl H Phenyl H 1d²⁸² Methyl Methyl CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1d²⁸³ Methyl F CONH₂ 2-Methoxyethyl H Butyl H 1d²⁸⁴ Methyl F CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1d²⁸⁵ Methyl F CONH₂ 3-Methoxy propyl H Butyl H 1d²⁸⁶ Methyl F CONH₂ Butyl Butyl 2-Hydroxy ethyl H 1d²⁸⁷ Methyl F CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1d²⁸⁸ Methyl F CONH₂ 2-Fluoro ethyl H Butyl H 1d²⁸⁹ Methyl F CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1d²⁹⁰ Methyl F CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1d²⁹¹ Methyl F CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d²⁹² Methyl F CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d²⁹³ Methyl F CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1d²⁹⁴ Methyl F CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d²⁹⁵ Methyl F CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1d²⁹⁶ Methyl F CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1d²⁹⁷ Methyl F CONH₂ H H 3-(2-Hydroxy H ethoxy)ethyl 1d²⁹⁸ Methyl F CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1d²⁹⁹ Methyl F CONH₂ 3-(2-Hydroxy H H H ethoxy)ethyl 1d³⁰⁰ Methyl F CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d³⁰¹ Methyl F CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1d³⁰² Methyl F CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d³⁰³ Methyl F CONH₂ 3-Isopropoxy-propyl H H H 1d³⁰⁴ Methyl F CONH₂ 3-Isopropoxy-propyl H Phenyl H 1d³⁰⁵ Methyl F CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d³⁰⁶ Methyl F CONH₂ 3-Ethoxy-propyl H H H 1d³⁰⁷ Methyl F CONH₂ 3-Ethoxy-propyl H Phenyl H 1d³⁰⁸ Methyl F CONH₂ 3-Ethoxy butyl H 3-Ethoxybutyl H 1d³⁰⁹ Methyl F CONH₂ 3-Ethoxy butyl H H H 1d³¹⁰ Methyl F CONH₂ 3-Ethoxy butyl H Phenyl H 1d³¹¹ Methyl F CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl 1d³¹² NHCOCH₃ OMe CONH₂ 2-Methoxyethyl H Butyl H 1d³¹³ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H 3-Methoxy propyl H 1d³¹⁴ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1d³¹⁵ NHCOCH₃ OMe CONH₂ Butyl Butyl 2-Hydroxy ethyl H 1d³¹⁶ NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1d³¹⁷ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1d³¹⁸ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1d³¹⁹ NHCOCH₃ OMe CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1d³²⁰ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d³²¹ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d³²² NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1d³²³ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxyethoxy)ethyl H Butyl H 1d³²⁴ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy ethoxy) H propyl 1d³²⁵ NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1d³²⁶ NHCOCH₃ OMe CONH₂ H H 3-(2-Hydroxy H ethoxy)propyl 1d³²⁷ NHCOCH₃ OMe CONH₂ 2-(2-Hydroxy H H H ethoxy)ethyl 1d³²⁸ NHCOCH₃ OMe CONH₂ 3-(2-Hydroxy H H H ethoxy)propyl 1d³²⁹ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d³³⁰ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1d³³¹ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d³³² NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1d³³³ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1d³³⁴ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d³³⁵ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1d³³⁶ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1d³³⁷ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1d³³⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H H H 1d³³⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H Phenyl H 1d³⁴⁰ NHCOCH₃ OMe CONH₂ 3-Methoxy propyl H Butyl H 1d³⁴¹ NHCOCH₃ OMe CONH₂ Butyl Butyl 2-Hydroxy ethyl H 1d³⁴² NHCOCH₃ OMe CONH₂ Isopropyl Isopropyl 2-Hydroxy ethyl H 1d³⁴³ NHCOCH₃ OMe CONH₂ 2-Fluoro ethyl H Butyl H 1d³⁴⁴ NHCOCH₃ OMe CONH₂ 2-Chloro ethyl H 2-Ethyl hexyl H 1d³⁴⁵ NHCOCH₃ OMe CONH₂ 3-Chloro propyl H 2-Ethyl hexyl H 1d³⁴⁶ NHCOCH₃ OMe CONH₂ 2-(2- H Butyl H Hydroxyethylsulfanyl)- ethyl 1d³⁴⁷ NHCOCH₃ OMe CONH₂ 2-(2-tert-Butyl sulfanyl- H Butyl H ethane sulfonyl)-ethyl 1d³⁴⁸ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxy H Butyl H propyl 1d³⁴⁹ NHCOCH₃ OMe CONH₂ 2-Hydroxy ethoxyethyl H Butyl H 1d³⁵⁰ NHCOCH₃ OMe CONH₂ 2-(Ethyl sulfonyl) ethanol H Butyl H 1d³⁵¹ NHCOCH₃ OMe CONH₂ H H 3-(2-Hydroxy ethoxy) H propyl 1d³⁵² NHCOCH₃ OMe CONH₂ H H 2-(2-Hydroxy H ethoxy)ethyl 1d³⁵³ NHCOCH₃ OMe CONH₂ Phenyl H 2-(2-Hydroxy H ethoxy)ethyl 1d³⁵⁴ NHCOCH₃ OMe CONH₂ 3-(2-Phenoxy-ethoxy)- H H H propyl 1d³⁵⁵ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H 3-Isopropoxy-propyl H 1d³⁵⁶ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H H H 1d³⁵⁷ NHCOCH₃ OMe CONH₂ 3-Isopropoxy-propyl H Phenyl H 1d³⁵⁸ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H 3-Ethoxy-propyl H 1d³⁵⁹ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H H H 1d³⁶⁰ NHCOCH₃ OMe CONH₂ 3-Ethoxy-propyl H Phenyl H 1d³⁶¹ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H 3-Ethoxy butyl H 1d³⁶² NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H H H 1d³⁶³ NHCOCH₃ OMe CONH₂ 3-Ethoxy butyl H Phenyl H 1d³⁶⁴ NHCOCH₃ OMe CONH₂ 4-(2-Hydroxy- H H H ethanesulfonyl)-phenyl

The present invention also provides a process for the preparation of dyes of formula (1) and mixtures thereof as discribed above comprising the steps

a) diazotization of a compound of formula (2)

wherein R¹ to R⁴ are defined as given above, b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4)

wherein R⁹ to R¹² are defined as given above, to yield an intermediate of formula (5)

c) diazotization of the compound of formula (5), d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof

wherein R⁹ to R²⁰ are defined as given above.

The diazotization of the compound of the formula (2) and (5), respectively can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.

The coupling reaction of the diazonium salts obtained by diazotization of the compound of formula (2) onto the compounds of formulae (3) and (4) as well as the coupling reaction of the diazonium salts obtained by diazotization of the compound of formula (5) onto the compounds of formulae (6), (7), (8) and (9) can likewise be performed by known methods.

The compounds of formula (2) are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods dosclosed in DE79780, DE72665, DE61174 and U.S. Pat. No. 4,801,694 A1.

The pyridines of formula (6), (7), (8) and (9) in which R¹³ and R¹⁹ represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as DE2230392. Through analogy, all the diamino pyridines that are used in this patent can be synthesized with the protocol. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines of formula (6), (7), (8) and (9) in which R¹³ and R¹⁹ represent carbonamide or by hydrolysis and further esterification to form pyridines of formula (10), (11), (12) and (13) in which R¹³ and R¹⁹ are alkoxycarbonyl.

The above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alkohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40° C. to 150° C.

Alternatively, the above mentioned derivatization reactions can be undertaken as a final step after the synthesis of the corresponding dyes with pyridine nitriles.

The dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.

Also an aqueous solution for dying comprising one or more dye(s) as described above forms an aspect of the present invention.

The dyes of the present invention are suitable for dyeing and printing of natural, manufactured, regenerated, modified or synthetic hydroxyl- amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes.

Therefore, the present invention also is directed to a Process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye as described above.

The use of a dye as described above, a chemical composition as described above or of an aqueous solution as described above for dying fibers, as well as blends of such fibres selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers forms another aspect of the present invention.

Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.

The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet. For instance in the form of sheetlike structures, such as paper and leather, in the form of films, such as nylon films, or in the form of a bulk mass, for example composed of polyamide and polyurethane, in particular in the form of fibers, for example cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages.

The dyes of the present invention and their salts and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions. The di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.

Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, comparable fastness properties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.

It applies in particular to the production of dyeings on fiber materials composed of wool or other natural polyamides or of synthetic polyamides and their mixtures with other fiber material. In general, the material to be dyed is introduced into the bath at a temperature of about 40° C., agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98° C. However, the dyeings can also be carried out at the boil or in a sealed dyeing apparatus at temperatures of up to 106° C.

Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. For this the dyes of the present invention need to be formulated in aqueous inks.

An Ink for digital textile printing, comprising a dye of the present invention is another aspect of the present invention.

The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight and most preferably from 1 to 15% by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.

For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 to 50% by weight and preferably 5 to 30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1,2-ethanediol, 1,2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol, 1,4-pentanediol, 1,5-pentanediol, hexanediol, D,L-1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, N,N′-epsilon dimethylurea, ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane, dioxane, ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1,2-dimethoxypropane and trimethylpropane.

The inks of the present invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50° C. Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1,2-hexanediol.

The inks of the present invention may further comprise customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1% by weight based on the total weight of the ink.

The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind. Blend fabrics, for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.

In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. In addition there is a need for thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.

The examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.

EXAMPLE 1

7.96 g of 3,7-Diamino-naphthalene-1,5-disulfonic acid were first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when the temperature reached 10 to 15° C., 10.6 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8° C. when the mixture was added dropwise into 12.38 g of concentrated HCl with 12 g of ice. Yellow suspension was formed and the reaction mixture was completed within an hour.

6.30 g of 2,5-Dimethyl-phenylamine were added directly into the diazo suspension and stirred. A violet precipitate was observed upon addition. The intermediate precipitate, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic acid obtained was filtered off with suction, washed with organic solvent and dried.

15.22 g of the dried intermediate, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic acid, was then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when the temperature reached 10 to 15° C., 10.1 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8° C. when the mixture was added dropwise into concentrated HCl with ice. Violet suspension was formed and the reaction mixture was completed in 90 mins.

The obtained reaction mixture was used in the next step as described below: 14.62 g of 2,6-Bis-(3-methoxy-propylamino)-4-methyl-nicotinonitrile were stirred in methanol and adjusted to slightly acidic. The reaction mixture was added dropwise into the methanol solution and stirred. Brilliant orange precipitate was observed upon addition. The precipitate obtained was filtered off with suction and washed with brine giving the product of the formula 1a⁵². The analytic data are consistent with the assigned structure for product 1a⁵². The product dyes the targeted fibre materials in brilliant red to reddish violet shades.

Through analogy, all the dyes of formulae (1) can be synthesized according to the method described above.

Dyeing Example 1

1 part of the dye 1a⁵² of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98° C. over the course of 50 minutes and than dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 2

1 part of the dye 1a⁵² of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried.

The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 3

100 parts of polyamide-6 material were padded with a 1000 parts 50° C. liquor solution that consisted of 40 parts of the dye 1 m⁵², 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98° C. for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried.

The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 4

1 part of the dye 1a⁵² of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added. The pH was then adjusted to 4.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90° C. and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried.

The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 5

1 part of the dye 1a⁵² of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 part of a wetting agent (anionic) was added. 100 parts of bleached cotton knitted fabric were added to this solution. The dye bath was then heated up to 98° C. with a gradient of 2° C./min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80° C. At 80° C. the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 6

3 parts of the dye 1a⁵² of this invention dissolved in 82 parts of deionized water is added into the dyebath with 15 parts of diethylene glycol at 60° C. On cooling, a red printing ink is obtained. The red printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

Dyeing Example 7

4 parts of chemically bleached (pine wood) sulphite pulp is mixed up with 100 parts of 55° C. water. 1 part of the dye 1a⁵² of this invention is dissolved in 100 parts of hot water. 80 parts of this solution is given to the mixed-up pulp and mixed for 2 minutes. After that the mixture is sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution is then diluted with 2000 parts of cold water and the paper is produced out of this solution. The red paper produced from the mixture has good wet fastnesses. 

1.-17. (canceled)
 18. A dye of formula (1)

Wherein R¹, R², R³ and R⁴ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M—whereby at least two of them are SO₃M, R⁵, R⁶, R⁷ and R⁸ independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl-acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO₃M or alkylureido, R⁹ and R¹⁵ independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R¹⁰ and R¹⁶ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, acyloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R¹¹, R¹², R¹³, R¹⁴, R¹⁷, R¹⁸, R¹⁹, R²⁰ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, the dyes of formula (1) have two to six sulfonic acid groups, and whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R¹¹ and R¹², and R¹³ and R¹⁴, respectively can be positioned ortho or para to R⁹, meaning that when the amino rest bearing the substituents R¹¹ and R¹² is positioned ortho to R⁹, the amino rest bearing the substituents R¹³ and R¹⁴ is positioned para to R⁹, and vice versa; and the same applies to the amino rests bearing the substituents R¹⁷ and R¹⁸, and R¹⁹ to R²⁰, respectively that can be positioned ortho or para to R¹⁵, meaning that when the amino rest bearing the substituents R¹⁷ and R¹⁸ is positioned ortho to R¹⁵, the amino rest bearing the substituents R¹⁹ to R²⁰ is positioned para to R¹⁵, and vice versa.
 19. The dye according to claim 18, having formula (1a)

wherein R^(1a), R^(2a), R^(3a) and R^(4a) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9a) and R^(15a) independent of one another is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10a) and R^(16a) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents, R^(11a), R^(12a) R^(13a), R^(14a), R^(17a), R^(18a), R^(19a) and R^(20a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
 20. The dye according to claim 19, wherein R^(1a), R^(2a), R^(3a) and R^(4a) independent of each other is SO₃M, hydrogen, alkyl, alkoxy or halogen—whereby at least two of them are SO₃M, R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9a) and R^(15a) independent of each other is cyano or carbamoyl, R^(10a) and R^(16a) is methyl, R^(11a), R^(12a) R^(13a), R^(14a), R^(17a), R^(18a), R^(19a) and R^(20a) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, alkyl substituted by SO₃M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.
 21. The dye according to claim 18, having formula (1b)

wherein R^(1b), R^(2b), R^(3b) and R^(4b) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5b), R^(6b), R^(7b) and R^(8b) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9b) and R^(15b) independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl, R^(10b) and R^(16b) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstiuted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents, R^(11b), R^(12b) R^(13b), R^(14b), R^(17b), R^(18b), R^(19b) and R^(20b) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
 22. The dye according to claim 21, wherein R^(3b) and R^(4b) is SO₃M, R^(1b) and R^(2b) is hydrogen, R^(5b), R^(6b), R^(7b) and R^(8b) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9b) and R^(15b) independent of each other is cyano or carbamoyl, R^(10b) and R^(16b) is methyl, R^(11b), R^(12b) R^(13b), R^(14b), R^(17b), R^(18b), R^(19b) and R^(20b) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanyl-ethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO₃M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.
 23. The dye according to claim 18, having formula (1c)

wherein R^(1c), R^(2c), R^(3c) and R^(4c) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(5c), R^(6c), R^(7c) and R^(8c) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9c) and R^(15c) independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R^(10c) and R^(16c) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstiuted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents, R^(11c), R^(12c) R^(13c), R^(14c), R^(17c), R^(18c), R^(19c) and R^(20c) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkyl alkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
 24. The dye according to claim 23, wherein R^(2c) and R^(4c) is SO₃M, R^(1c) and R^(2c) is hydrogen, R^(5c), R^(6c), R^(7c) and R^(8c) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9c) and R^(15c) independent of each other is cyano or carbamoyl, R^(10c) and R^(16c) is methyl, R^(11c), R^(12c) R^(13c), R^(14c), R^(17c), R^(18c), R^(19c) and R^(20c) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tort-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO₃M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.
 25. The dye according to claim 18, having formula (1d)

wherein R^(1d), R^(2d), R^(3d) and R^(4d) independent of each other is hydrogen, alkyl, alkoxy, halogen, Preliminary Amendment trifluoromethyl or SO₃M whereby at least two of them are SO₃M, R^(5d), R^(6d), R^(7d) and R^(8d) independent of each other is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl, —SO₃M or (C₁-C₄)-acylamino, R^(9d) and R^(15d) independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl, R^(10d) and R^(16d) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstiuted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl with one or more substituents, R^(11d), R^(12d) R^(13d), R^(14d), R^(17d), R^(18d), R^(19d) and R^(20d) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
 26. The dye according to claim 25, wherein R^(1d) and R^(3d) is SO₃M, R^(2d) and R^(4d) is hydrogen, R^(5d), R^(6d), R^(7d) and R^(8d) independent of each other is hydrogen, methyl, halogen, —SO₃M or acetylamino, R^(9d) and R^(15d) independent of each other is cyano or carbamoyl, R^(10d) and R^(16d) is methyl, R^(11d), R^(12d) R^(13d), R^(14d), R^(17d), R^(18d), R^(19d) and R^(20d) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO₃M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.
 27. A process for the preparation of the dye according to claim 18 and mixtures thereof comprising the steps a) diazotization of a compound of formula (2)

wherein R¹ to R⁴ are defined as M claim 18, b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4)

wherein R⁵ to R⁸ are defined as in claim 18, to yield an intermediate of formula (5)

c) diazotization of the compound of formula (5), d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof

wherein R¹¹ to R²⁰ are defined as in claim
 18. 28. A chemical composition comprising one or more dye(s) according to claim
 18. 29. A chemical composition consisting essentially of two or more dyes according to claim
 18. 30. Aqueous solution for dying comprising one or more chemical compounds according to claim
 18. 31. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim
 18. 32. An ink for digital textile printing, comprising the dye according to claim
 18. 33. A fiber and blends containing the fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) according to claim 18 either in chemically and/or physically bound form. 